Methods for producing a total product in the presence of sulfur

ABSTRACT

Methods of producing a total product are described. A method includes continuously contacting a feed with a hydrogen source in the presence of one or more inorganic salt catalysts and steam to produce a total product, wherein the feed has at least 0.02 grams of sulfur, per gram of feed; and producing a total product that includes coke and the crude product. The crude product has a sulfur content of at most 90% of the sulfur content of the feed.

PRIORITY

This application is a continuation-in-part application claiming priorityto U.S. patent application Ser. No. 11/014,299 filed Dec. 16, 2004,which claims priority to U.S. Provisional Patent Application No.60/531,506 filed Dec. 19, 2003 and U.S. Provisional Patent ApplicationNo. 60/618,814 filed Oct. 14, 2004.

FIELD OF THE INVENTION

The present invention generally relates to systems and methods fortreating feed, and to compositions that are produced, for example, usingsuch systems and methods.

DESCRIPTION OF RELATED ART

Crudes that have one or more unsuitable properties that do not allow thecrudes to be economically transported, or processed using conventionalfacilities, are commonly referred to as “disadvantaged crudes”.

Disadvantaged crudes often contain relatively high levels of residue.Such crudes tend to be difficult and expensive to transport and/orprocess using conventional facilities. High residue crudes may betreated at high temperatures to convert the crude to coke.Alternatively, high residue crudes are typically treated with water athigh temperatures to produce less viscous crudes and/or crude mixtures.During processing, water removal from the less viscous crudes and/orcrude mixtures may be difficult using conventional means.

Disadvantaged crudes may include hydrogen deficient hydrocarbons. Whenprocessing hydrogen deficient hydrocarbons, consistent quantities ofhydrogen generally need to be added, particularly if unsaturatedfragments resulting from cracking processes are produced. Hydrogenationduring processing, which typically involves the use of an activehydrogenation catalyst, may also be needed to inhibit unsaturatedfragments from forming coke. Processes such as reforming that are usedto produce hydrogen are generally endothermic and, typically, requireadditional heat. Hydrogen and/or heat is costly to produce and/or costlyto transport to treatment facilities.

Coke may form and/or deposit on catalyst surfaces at a rapid rate duringprocessing of disadvantaged crudes. It may be costly to regenerate thecatalytic activity of a catalyst contaminated by coke. High temperaturesused during regeneration may also diminish the activity of the catalystand/or cause the catalyst to deteriorate.

Disadvantaged crudes may include acidic components that contribute tothe total acid number (“TAN”) of the feed. Disadvantaged crudes with arelatively high TAN may contribute to corrosion of metal componentsduring transporting and/or processing of the disadvantaged crudes.Removal of acidic components from disadvantaged crudes may involvechemically neutralizing acidic components with various bases.Alternately, corrosion-resistant metals may be used in transportationequipment and/or processing equipment. The use of corrosion-resistantmetal often involves significant expense, and thus, the use ofcorrosion-resistant metal in existing equipment may not be desirable.Another method to inhibit corrosion may involve addition of corrosioninhibitors to disadvantaged crudes before transporting and/or processingof the disadvantaged crudes. The use of corrosion inhibitors maynegatively affect equipment used to process the crudes and/or thequality of products produced from the crudes.

Disadvantaged crudes may contain relatively high amounts of metalcontaminants, for example, nickel, vanadium, and/or iron. Duringprocessing of such crudes, metal contaminants, and/or compounds of metalcontaminants, may deposit on a surface of the catalyst or the voidvolume of the catalyst. Such deposits may cause a decline in theactivity of the catalyst.

Disadvantaged crudes often include organically bound heteroatoms (forexample, sulfur, oxygen, and nitrogen). Organically bound heteroatomsmay, in some situations, have an adverse effect on catalysts. Alkalimetal salts and/or alkaline-earth metal salts have been used inprocesses for desulfurization of residue. These processes tend to resultin poor desulfurization efficiency, production of oil insoluble sludge,poor demetallization efficiency, formation of substantially inseparablesalt-oil mixtures, utilization of large quantities of hydrogen gas,and/or relatively high hydrogen pressures.

Some processes for improving the quality of crude include adding adiluent to disadvantaged crudes to lower the weight percent ofcomponents contributing to the disadvantaged properties. Adding diluent,however, generally increases costs of treating disadvantaged crudes dueto the costs of diluent and/or increased costs to handle thedisadvantaged crudes. Addition of diluent to a disadvantaged crude may,in some situations, decrease stability of such crude.

U.S. Pat. No. 3,847,797 to Pasternak et al.; U.S. Pat. No. 3,948,759 toKing et al.; U.S. Pat. No. 3,957,620 to Fukui et al.; U.S. Pat. No.3,960,706 to McCollum et al.; U.S. Pat. No. 3,960,708 to McCollum etal.; U.S. Pat. No. 4,119,528 to Baird, Jr. et al.; U.S. Pat. No.4,127,470 to Baird, Jr. et al.; U.S. Pat. No. 4,437,980 to Heredy etal.; and U.S. Pat. No. 4,665,261 to Mazurek; all of which areincorporated herein by reference, describe various processes and systemsused to treat crudes. U.S. Published Application Nos. 20050133405;20050133406; 20050135997; 20050139512; 20050145536; 20050145537;20050145538; 20050155906; 20050167321; 20050167322; 20050167323;20050170952; and 20050173298 to Wellington et al. all of which areincorporated herein by reference, describe contact of a feed in thepresence of a catalyst to produce a crude product. The process, systems,and catalysts described in these patents, however, have limitedapplicability because of many of the technical problems set forth above.

In sum, disadvantaged crudes generally have undesirable properties (forexample, relatively high residue, a tendency to corrode equipment,and/or a tendency to consume relatively large amounts of hydrogen duringtreatment). Other undesirable properties include relatively high amountsof undesirable components (for example, relatively high TAN, organicallybound heteroatoms, and/or metal contaminants). Such properties tend tocause problems in conventional transportation and/or treatmentfacilities, including increased corrosion, decreased catalyst life,process plugging, and/or increased usage of hydrogen during treatment.Thus, there is a significant economic and technical need for improvedsystems, methods, and/or catalysts for conversion of disadvantagedcrudes into crude products with properties that are more desirable.

SUMMARY OF THE INVENTION

Inventions described herein generally relate to systems and methods forcontacting a feed with one or more catalysts to produce a total productcomprising a crude product and, in some embodiments, non-condensablegas. Inventions described herein also generally relate to compositionsthat have novel combinations of components therein. Such compositionscan be obtained by using the systems and methods described herein.

In certain embodiments, the invention provides a system for producing atotal product, comprising: a contacting zone, the contacting zone beingconfigured to fluidize a supported inorganic salt catalyst in thepresence of a feed, steam and a hydrogen source to produce the totalproduct; a regeneration zone configured to receive at least a portion ofthe supported inorganic salt catalyst from the contacting zone andremove at least a portion of contaminants from the supported inorganicsalt catalyst; and a recovery zone, the recovery zone being configuredto receive combustion gas from the regeneration zone, wherein therecovery zone is configured to separate at least a portion of inorganicsalts from the combustion gas.

In certain embodiments, the invention provides a method of producingtotal product, comprising: providing a feed to a contacting zone;providing an inorganic salt catalyst to the contacting zone; contactingthe inorganic salt catalyst with the feed in the presence of a hydrogensource and steam in the contacting zone; producing a total product and aused inorganic salt catalyst; heating the used inorganic salt catalystto remove at least a portion of contaminants from the inorganic saltcatalyst, wherein a combustion gas is produced during the heating of theused inorganic salt catalyst; and recovering inorganic salts from thecombustion gas.

In certain embodiments, the invention provides a method of producingtotal product, comprising: providing a feed to a contacting zone;providing an inorganic salt catalyst to the contacting zone; contactingthe inorganic salt catalyst with the feed in the presence of a hydrogensource and steam such that the inorganic salt catalyst becomes fluidizedin the contacting zone; and producing a total product.

In certain embodiments, the invention provides a method of producing atotal product, comprising: providing a feed to a contacting zone;providing a supported inorganic salt catalyst to the contacting zone;contacting the supported inorganic salt catalyst with the feed in thepresence of a hydrogen source and steam in the contacting zone; andproducing the total product.

In certain embodiments, the invention provides a method of producing acrude product, comprising: providing a feed to a contacting zone,wherein the feed has at total content, per gram of feed, of at least 0.9grams of hydrocarbons having a boiling range distribution between 343°C. and 538° C.; providing a supported inorganic salt catalyst to thecontacting zone; contacting the supported inorganic salt catalyst withthe feed in the presence of a hydrogen source and steam such that thesupported inorganic salt catalyst becomes fluidized; and producing atotal product that includes a crude product, and the crude producthaving a total content of at least 0.2 grams per gram of crude productof hydrocarbon have a boiling range distribution between 204° C. and343° C.

In certain embodiments, the invention provides a method of producing atotal product, comprising: contacting a feed with a hydrogen source inthe presence of one or more inorganic salt catalysts and steam toproduce a total product; and controlling contacting conditions such thatthe conversion of feed to hydrocarbon gas and hydrocarbon liquid isbetween 5% and 50%, based on the molar amount of carbon in the feed.

In certain embodiments, the invention provides a method of producing atotal product, comprising: contacting a feed with light hydrocarbons inthe presence of one or more inorganic salt catalysts and steam toproduce a total product; and controlling contacting conditions such thatat least 50% of the light hydrocarbons are recovered; and producing atotal product, wherein a ratio of atomic hydrogen to carbon (H/C) in thetotal product is between 80% and 120% of the atomic H/C of the feed.

In certain embodiments, the invention provides a method of producing atotal product, comprising: providing a feed to a contacting zone;providing a supported inorganic salt catalyst to the contacting zone;contacting the supported inorganic salt catalyst with the feed in thepresence of a hydrogen source and steam in the contacting zone at atemperature of at most 1000° C. and a total operating pressure of atmost 4 MPa; and producing the total product.

In certain embodiments, the invention provides a method of producing atotal product, comprising: continuously contacting a feed with ahydrogen source in the presence of one or more inorganic salt catalystsand steam to produce a total product, wherein the feed has at least 0.02grams of sulfur, per gram of feed; and producing a total product thatincludes that includes coke and the crude product, wherein the crudeproduct has a sulfur content of at most 90% of the sulfur content of thefeed and the content of coke is at most 0.2 grams, per gram of feed.

In further embodiments, features from specific embodiments may becombined with features from other embodiments. For example, featuresfrom the any one of the series of embodiments may be combined withfeatures from any of the other series of embodiments.

In further embodiments, total products are obtainable by any of themethods and systems described herein.

In further embodiments, additional features may be added to the specificembodiments described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

Advantages of the present invention will become apparent to thoseskilled in the art with the benefit of the following detaileddescription and upon reference to the accompanying drawings in which:

FIG. 1 is a schematic of an embodiment of a contacting system forcontacting the feed with a hydrogen source in the presence of one ormore catalysts to produce the total product.

FIG. 2 is a schematic of another embodiment of a contacting system forcontacting the feed with a hydrogen source in the presence of one ormore catalysts to produce the total product.

FIG. 3 is a schematic of an embodiment of a contacting system forfluidly contacting the feed with a hydrogen source in the presence ofone or more catalyst to produce the total product.

FIG. 4 is a schematic of another embodiment of a contacting system forfluidly contacting the feed with a hydrogen source in the presence ofone or more catalyst to produce the total product.

FIG. 5 is a schematic of an embodiment of a separation zone incombination with a contacting system.

FIG. 6 is a schematic of an embodiment of a blending zone in combinationwith a contacting system.

FIG. 7 is a schematic of an embodiment of a separation zone, acontacting system, and a blending zone.

FIG. 8 is a schematic of an embodiment of multiple contacting systems.

FIG. 9 is a schematic of an embodiment of an ionic conductivitymeasurement system.

FIG. 10 is a graphical representation of log 10 plots of ion currents ofemitted gases of an inorganic salt catalyst versus temperature, asdetermined by TAP.

FIG. 11 is a graphic representation of log plots of the resistance ofinorganic salt catalysts and an inorganic salt relative to theresistance of potassium carbonate versus temperature.

FIG. 12 is a graphic representation of log plots of the resistance of aNa₂CO₃/K₂CO₃/Rb₂CO₃ catalyst relative to resistance of the potassiumcarbonate versus temperature.

FIG. 13 is a graphical representation of weight percent of coke, liquidhydrocarbons, and gas versus various hydrogen sources produced fromembodiments of contacting the feed with the inorganic salt catalyst.

FIG. 14 is a graphical representation of weight percentage versus carbonnumber of crude products produced from embodiments of contacting thefeed with the inorganic salt catalyst.

FIG. 15 is a tabulation of components produced from embodiments ofcontacting the feed with inorganic salt catalysts, a metal salt, orsilicon carbide.

FIG. 16 is a graphical representation of product selectivity versuscalcium oxide, magnesium oxide, zirconium oxide, and silicon carbide.

FIG. 17 is a tabulation of components produced from embodiments ofcontacting the feed with a supported inorganic salt catalyst and anE-Cat.

FIG. 18 is a graphical representation of components produced fromembodiments of contacting the feed with a supported inorganic saltcatalyst and an E-Cat.

While the invention is susceptible to various modifications andalternative forms, specific embodiments thereof are shown by way ofexample in the drawings and will herein be described in detail. Thedrawings may not be to scale. It should be understood that the drawingsand detailed description thereto are not intended to limit the inventionto the particular form disclosed, but on the contrary, the intention isto cover all modifications, equivalents, and alternatives falling withinthe spirit and scope of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The above problems may be addressed using systems, methods, andcatalysts described herein. For example, a feed and an inorganic saltcatalyst may be provided to a contacting zone. Contact of the inorganicsalt catalyst with the feed may be performed such that the inorganicsalt catalyst becomes fluidized in the contacting zone and a totalproduct is produced.

Certain embodiments of the inventions are described herein in moredetail. Terms used herein are defined as follows.

“Alkali metal(s)” refer to one or more metals from Column 1 of thePeriodic Table, one or more compounds of one or more metals from Column1 of the Periodic Table, or mixtures thereof.

“Alkaline-earth metal(s)” refer to one or more metals from Column 2 ofthe Periodic Table, one or more compounds of one or more metals fromColumn 2 of the Periodic Table, or mixtures thereof.

“AMU” refers to atomic mass unit.

“ASTM” refers to American Standard Testing and Materials.

“Asphaltenes” refers to organic materials that are found in crudes thatare not soluble in straight-chain hydrocarbons such as n-pentane orn-heptane. Asphaltene, in some embodiments, include aromatic andnaphthenic ring compounds containing heteroatoms.

Atomic hydrogen percentage and atomic carbon percentage of feed, crudeproduct, naphtha, kerosene, diesel, and VGO are as determined by ASTMMethod D5291.

“API gravity” refers to API gravity at 15.5° C. API gravity is asdetermined by ASTM Method D6822.

“Bitumen” refers to one type of crude produced and/or retorted from ahydrocarbon formation.

Boiling range distributions for the feed and/or total product are asdetermined by ASTM Methods D5307, unless otherwise mentioned. Content ofhydrocarbon components, for example, paraffins, iso-paraffins, olefins,naphthenes and aromatics in naphtha are as determined by ASTM MethodD6730. Content of aromatics in diesel and VGO is as determined by IPMethod 368/90. Content of aromatics in kerosene is as determined by ASTMMethod D5186.

“Brønsted-Lowry acid” refers to a molecular entity with the ability todonate a proton to another molecular entity.

“Brønsted-Lowry base” refers to a molecular entity that is capable ofaccepting protons from another molecular entity. Examples ofBrønsted-Lowry bases include hydroxide (OH⁻), water (H₂O), carboxylate(RCO₂ ⁻), halide (Br⁻, Cl⁻, F⁻, I⁻), bisulfate (HSO₄ ⁻), and sulfate(SO₄ ²⁻).

“Catalyst” refers to one or more supported catalysts, one or moreunsupported catalysts, or mixtures thereof.

“Carbon number” refers to the total number of carbon atoms in amolecule.

“Coke” refers to solids containing carbonaceous solids that are notvaporized under process conditions. The content of coke is as determinedby mass balance. The weight of coke is the total weight of solid minusthe total weight of input catalysts.

“Content” refers to the weight of a component in a substrate (forexample, a crude, a total product, or a crude product) expressed asweight fraction or weight percentage based on the total weight of thesubstrate. “Wtppm” refers to parts per million by weight.

“Diesel” refers to hydrocarbons with a boiling range distributionbetween 260° C. and 343° C. (500-650° F.) at 0.101 MPa. Diesel contentis as determined by ASTM Method D2887.

“Distillate” refers to hydrocarbons with a boiling range distributionbetween 204° C. and 343° C. (400-650° F.) at 0.101 MPa. Distillatecontent is as determined by ASTM Method D2887. Distillate may includekerosene and diesel.

“DSC” refers to differential scanning calorimetry.

“Feed” refers to a crude, disadvantaged crude, a mixture ofhydrocarbons, or combinations thereof that are to be treated asdescribed herein.

“Freeze point” and “freezing point” refer to the temperature at whichformation of crystalline particles occurs in a liquid. A freezing pointis as determined by ASTM D2386.

“GC/MS” refers to gas chromatography in combination with massspectrometry.

“Hard base” refers to anions as described by Pearson in Journal ofAmerican Chemical Society, 1963, 85, p. 3533, which is incorporated byreference herein.

“H/C” refers to a weight ratio of atomic hydrogen to atomic carbon. H/Cis as determined from the values measured for weight percentage ofhydrogen and weight percentage of carbon by ASTM Method D5291.

“Heteroatoms” refer to oxygen, nitrogen, and/or sulfur contained in themolecular structure of a hydrocarbon. Heteroatoms content is asdetermined by ASTM Methods E385 for oxygen, D5762 for nitrogen, andD4294 for sulfur.

“Hydrogen source” refers to hydrogen, and/or a compound and/or compoundswhen in the presence of a feed and the catalyst react to providehydrogen to one or more compounds in the feed. A hydrogen source mayinclude, but is not limited to, hydrocarbons (for example, C₁ to C₆hydrocarbons such as methane, ethane, propane, butane, pentane,naphtha), water, or mixtures thereof. A mass balance is conducted toassess the net amount of hydrogen provided to one or more compounds inthe feed.

“Inorganic salt” refers to a compound that is composed of a metal cationand an anion.

“IP” refers to the Institute of Petroleum, now the Energy Institute ofLondon, United Kingdom.

“Iso-paraffins” refer to branched-chain saturated hydrocarbons.

“Kerosene” refers to hydrocarbons with a boiling range distributionbetween about 204° C. and about 260° C. (400-500° F.) at 0.101 MPa.Kerosene content is as determined by ASTM Method D2887.

“Lewis acid” refers to a compound or a material with the ability toaccept one or more electrons from another compound.

“Lewis base” refers to a compound and/or material with the ability todonate one or more electrons to another compound.

“Light Hydrocarbons” refer to hydrocarbons having carbon numbers in arange from 1 to 6.

“Liquid mixture” refers to a composition that includes one or morecompounds that are liquid at standard temperature and pressure (25° C.,0.101 MPa, hereinafter referred to as “STP”), or a composition thatincludes a combination of one or more compounds that are liquid at STPwith one or more compounds that are solid at STP.

“Micro-Carbon Residue” (“MCR”) refers to a quantity of carbon residueremaining after evaporation and pyrolysis of a substance. MCR content isas determined by ASTM Method D4530.

“Naphtha” refers to hydrocarbon components with a boiling rangedistribution between 38° C. and 204° C. (100-400° F.) at 0.101 MPa.Naphtha content is as determined by ASTM Method D2887.

“Ni/V/Fe” refers to nickel, vanadium, iron, or combinations thereof.

“Ni/V/Fe content” refers to Ni/V/Fe content in a substrate. Ni/V/Fecontent is as determined by ASTM Method D5863.

“Nm³/m³” refers to normal cubic meters of gas per cubic meter of feed.

“Nonacidic” refers to Lewis base and/or Brønsted-Lowry base properties.

“Non-condensable gas” refers to components and/or a mixture ofcomponents that are gases at standard temperature and pressure (25° C.,0.101 MPa, hereinafter referred to as “STP”).

“n-Paraffins” refer to normal (straight chain) saturated hydrocarbons.

“Octane number” refers to a calculated numerical representation of theantiknock properties of a motor fuel compared to a standard referencefuel. A calculated octane number of naphtha is as determined by ASTMMethod D6730.

“Olefins” refer to compounds with non-aromatic carbon-carbon doublebonds. Types of olefins include, but are not limited to, cis, trans,terminal, internal, branched, and linear.

“Periodic Table” refers to the Periodic Table as specified by theInternational Union of Pure and Applied Chemistry (IUPAC), November2003.

“Polyaromatic compounds” refer to compounds that include two or morearomatic rings. Examples of polyaromatic compounds include, but are notlimited to, indene, naphthalene, anthracene, phenanthrene,benzothiophene, and dibenzothiophene.

“Residue” refers to components that have a boiling range distributionabove 538° C. (1000° F.) at 0.101 MPa, as determined by ASTM MethodD5307.

“Semiliquid” refers to a phase of a substance that has properties of aliquid phase and a solid phase of the substance. Examples of semiliquidinorganic salt catalysts include a slurry and/or a phase that has aconsistency of, for example, taffy, dough, or toothpaste.

“SCFB” refers to standard cubic feet of gas per barrel of feed.

“Spent hydroprocessing catalyst” refers to any catalyst that is nolonger considered acceptable for use in a hydrotreating and/or ahydrocracking catalytic process. Spent hydroprocessing catalystsinclude, but are not limited to, nickel sulfide, vanadium sulfide,and/or molybdenum sulfide.

“Superbase” refers to a material that can deprotonate hydrocarbons suchas paraffins and olefins under reaction conditions.

“TAN” refers to a total acid number expressed as milligrams (“mg”) ofKOH per gram (“g”) of sample. TAN is as determined by ASTM Method D664.

“TAP” refers to temporal-analysis-of-products.

“VGO” refers to components with a boiling range distribution betweenabout 343° C. and about 538° C. (650-1000° F.) at 0.101 MPa. VGO contentis as determined by ASTM Method D2887.

“WHSV” refers to a weight of feed/unit time divided by a volume ofcatalyst expressed as hours⁻¹.

All referenced methods are incorporated herein by reference. In thecontext of this application, it is to be understood that if the valueobtained for a property of the composition tested is outside of thelimits of the test method, the test method may be recalibrated to testfor such property. It should be understood that other standardizedtesting methods that are considered equivalent to the referenced testingmethods may be used.

Crudes may be produced and/or retorted from hydrocarbon containingformations and then stabilized. Crudes are generally solid, semi-solid,and/or liquid. Crudes may include crude oil. Stabilization may include,but is not limited to, removal of non-condensable gases, water, salts,or combinations thereof, from the crude to form a stabilized crude. Suchstabilization may often occur at, or proximate to, the production and/orretorting site.

Stabilized crudes typically have not been distilled and/or fractionallydistilled in a treatment facility to produce multiple components withspecific boiling range distributions (for example, naphtha, distillates,VGO, and/or lubricating oils). Distillation includes, but is not limitedto, atmospheric distillation methods and/or vacuum distillation methods.Undistilled and/or unfractionated stabilized crudes may includecomponents that have a carbon number above 4 in quantities of at least0.5 grams of components per gram of crude. Examples of stabilized crudesinclude whole crudes, topped crudes, desalted crudes, desalted toppedcrudes, or combinations thereof. “Topped” refers to a crude that hasbeen treated such that at least some of the components that have aboiling point below 35° C. at 0.101 MPa are removed. Typically, toppedcrudes have a content of at most 0.1 grams, at most 0.05 grams, or atmost 0.02 grams of such components per gram of the topped crude.

Some stabilized crudes have properties that allow the stabilized crudesto be transported to conventional treatment facilities by transportationcarriers (for example, pipelines, trucks, or ships). Other crudes haveone or more unsuitable properties that render them disadvantaged.Disadvantaged crudes may be unacceptable to a transportation carrier,and/or a treatment facility, thus imparting a low economic value to thedisadvantaged crude. The economic value may be such that a reservoirthat includes the disadvantaged crude that is deemed too costly toproduce, transport, and/or treat.

Properties of disadvantaged crudes may include, but are not limited to:a) TAN of at least 0.5; b) viscosity of at least about 0.2 Pa·s; c) APIgravity of at most 19; d) a total Ni/V/Fe content of at least 0.00005grams or at least 0.0001 grams of Ni/V/Fe per gram of crude; e) a totalheteroatoms content of at least 0.005 grams of heteroatoms per gram ofcrude; f) a residue content of at least 0.01 grams of residue per gramof crude; g) an asphaltenes content of at least 0.04 grams ofasphaltenes per gram of crude; h) a MCR content of at least 0.02 gramsof MCR per gram of crude; or i) combinations thereof. In someembodiments, disadvantaged crude may include, per gram of disadvantagedcrude, at least 0.2 grams of residue, at least 0.3 grams of residue, atleast 0.5 grams of residue, or at least 0.9 grams of residue. In certainembodiments, disadvantaged crude has about 0.2-0.99 grams, about 0.3-0.9grams, or about 0.4-0.7 grams of residue per gram of disadvantagedcrude. In certain embodiments, disadvantaged crudes, per gram ofdisadvantaged crude, may have a sulfur content of at least 0.001 grams,at least 0.005 grams, at least 0.01 grams, at least 0.02 grams, at least0.03 grams, or at least 0.04 grams. In some embodiments, disadvantagedcrudes may have a nitrogen content of at least 0.001 grams, at least0.005 grams, at least 0.01 grams, or at least 0.02 grams per gram ofdisadvantaged crude.

Disadvantaged crudes may include a mixture of hydrocarbons having arange of boiling points. Disadvantaged crudes may include, per gram ofdisadvantaged crude: at least 0.001 grams, at least 0.005 grams, or atleast 0.01 grams of hydrocarbons with a boiling range distributionbetween about 200° C. and about 300° C. at 0.101 MPa; at least 0.001grams, at least 0.005 grams, or at least 0.01 grams of hydrocarbons witha boiling range distribution between about 300° C. and about 400° C. at0.101 MPa; and at least 0.001 grams, at least 0.005 grams, or at least0.01 grams of hydrocarbons with a boiling range distribution betweenabout 400° C. and about 700° C. at 0.101 MPa, or combinations thereof.

In some embodiments, disadvantaged crudes may also include, per gram ofdisadvantaged crude, at least 0.001 grams, at least 0.005 grams, or atleast 0.01 grams of hydrocarbons with a boiling range distribution of atmost 200° C. at 0.101 MPa in addition to higher boiling components.Typically, the disadvantaged crude has, per gram of disadvantaged crude,a content of such hydrocarbons of at most 0.2 grams, or at most 0.1grams.

In certain embodiments, disadvantaged crudes may include, per gram ofdisadvantaged crude, up to 0.9 grams, or up to 0.99 grams ofhydrocarbons with a boiling range distribution of at least 300° C. Incertain embodiments, disadvantaged crudes may also include, per gram ofdisadvantaged crude, at least 0.001 grams of hydrocarbons with a boilingrange distribution of at least 650° C. In certain embodiments,disadvantaged crudes may include, per gram of disadvantaged crude, up toabout 0.9 grams, or up to about 0.99 grams of hydrocarbons with aboiling range distribution between about 300° C. and about 1000° C. Insome embodiments, disadvantaged crudes include at least 0.1 grams, atleast 0.5 grams, at least 0.8 grams, or at least 0.99 grams ofasphaltenes per gram of disadvantaged crude. Disadvantaged crudes mayinclude from about 0.01 grams to about 0.99 grams, from about 0.1 gramsto about 0.9 grams, or from about 0.5 grams to about 0.8 grams ofasphaltenes per gram of disadvantage crude. Examples of disadvantagedcrudes that can be treated using the processes described herein include,but are not limited to, crudes from the following countries and regionsof those countries: Canadian Alberta, Venezuelan Orinoco, U.S. southernCalifornian and north slope Alaska, Mexico Bay of Campeche, ArgentineanSan Jorge basin, Brazilian Santos and Campos basins, China Bohai Gulf,China Karamay, Iraq Zagros, Kazakhstan Caspian, Nigeria Offshore, UnitedKingdom North Sea, Madagascar northwest, Oman, and NetherlandsSchoonebek.

Treatment of disadvantaged crudes may enhance the properties of thedisadvantaged crudes such that the crudes are acceptable fortransportation and/or treatment. The feed may be topped as describedherein. The crude product resulting from treatment of the feed, usingmethods described herein is suitable for transporting and/or refining.Properties of the crude product are closer to the correspondingproperties of West Texas Intermediate crude than the feed, or closer tothe corresponding properties of Brent crude than the feed, and therebyhave enhanced economic value relative to the economic value of the feed.Such crude product may be refined with less or no pre-treatment, therebyenhancing refining efficiencies. Pre-treatment may includedesulfurization, demetallization, and/or atmospheric distillation toremove impurities from the crude product.

Methods of contacting a feed in accordance with inventions are describedherein. Additionally, embodiments to produce products with variousconcentrations of naphtha, kerosene, diesel, and/or VGO, which are notgenerally produced in conventional types of processes, are described.

In some embodiments, feeds that have boiling point distributions fromabout 10° C. to 1200° C. (for example, asphaltenes, VGO, kerosene,diesel, naphtha, or mixtures thereof) may be contacted in accordancewith the systems, methods and catalysts described herein. The feed mayinclude, per gram of feed, at least 0.01 grams, at least 0.1 grams, atleast 0.5 grams or at least 0.9 grams of a mixture of hydrocarbonshaving boiling point distributions with an initial boiling point above538° C. In some embodiments, the feed may include, per gram of feed,from about 0.01 grams to about 0.9 grams, from about 0.1 grams to about0.8 grams, from about 0.5 grams to about 0.7 grams of a mixture ofhydrocarbons having boiling point distributions with an initial boilingpoint above 538° C.

Hydrocarbon mixtures that have at least 0.01 grams, at least 0.1 grams,at least 0.5 grams, at least 0.8 grams, or at least 0.99 grams of VGOper gram of hydrocarbon mixture, may be treated in accordance with thesystem and methods described herein to produce various amounts ofnaphtha, kerosene, diesel, or distillate. A hydrocarbon mixture having,per gram of hydrocarbon mixture, from about 0.01 grams to about 0.99grams, from about 0.05 grams to about 0.9 grams, from about 0.1 grams toabout 0.8 grams, from about 0.2 grams to about 0.7 grams, or from about0.3 grams to about 0.6 grams of VGO may be treated to produce variousproducts having a boiling point distribution lower than the boilingpoint distribution of VGO.

The feed may be contacted with a hydrogen source in the presence of oneor more of the catalysts in a contacting zone and/or in combinations oftwo or more contacting zones.

In some embodiments, the hydrogen source is generated in situ. In situgeneration of the hydrogen source may include the reaction of at least aportion of the feed with the inorganic salt catalyst at temperatures ina range from about 200-1200° C., about 300-1000° C., about 400-900° C.,or about 500-800° C. to form hydrogen and/or light hydrocarbons. In situgeneration of hydrogen may include the reaction of at least a portion ofthe inorganic salt catalyst that includes, for example, alkali metalformate.

The total product generally includes gas, vapor, liquids, or mixturesthereof produced during the contacting. The total product includes thecrude product that is a liquid mixture at STP and, in some embodiments,hydrocarbons that are not condensable at STP. In some embodiments, thetotal product and/or the crude product may include solids (such asinorganic solids and/or coke). In certain embodiments, the solids may beentrained in the liquid and/or vapor produced during contacting.

A contacting zone typically includes a reactor, a portion of a reactor,multiple portions of a reactor, or multiple reactors. Examples ofreactors that may be used to contact a feed with a hydrogen source inthe presence of catalyst include a stacked bed reactor, a fixed bedreactor, a continuously stirred tank reactor (CSTR), a spray reactor, aplug-flow reactor, and a liquid/liquid contactor. Examples of a CSTRinclude a fluidized bed reactor and an ebullating bed reactor.

Contacting conditions typically include temperature, pressure, feedflow, total product flow, residence time, hydrogen source flow, orcombinations thereof. Contacting conditions may be controlled to producea crude product with specified properties.

Contacting temperatures may range from about 200-800° C., about 300-700°C., or about 400-600° C. In embodiments in which the hydrogen source issupplied as a gas (for example, hydrogen gas, methane, or ethane), aratio of the gas to the feed will generally range from about 1-16,100Nm³/m³, about 2-8000 Nm³/m³, about 3-4000 Nm³/m³, or about 5-320 Nm³/m³.Contacting typically takes place in a pressure range between about0.1-20 MPa, about 1-16 MPa, about 2-10 MPa, or about 4-8 MPa. In someembodiments in which steam is added, a ratio of steam to feed is in arange from about 0.01-10 kilograms, about 0.03-5 kilograms, or about0.1-1 kilogram of steam, per kilogram of feed. A flow rate of feed maybe sufficient to maintain the volume of feed in the contacting zone ofat least 10%, at least 50%, or at least 90% of the total volume of thecontacting zone. Typically, the volume of feed in the contacting zone isabout 40%, about 60%, or about 80% of the total volume of the contactingzone. In some embodiments, WHSV in a contacting zone ranges from about0.1 to about 30 h⁻¹, about 0.5 to about 20 h⁻¹, or about 1 to about 10h⁻¹. In some embodiments, contacting may be done in the presence of anadditional gas, for example, argon, nitrogen, methane, ethane, propanes,butanes, propenes, butenes, or combinations thereof.

FIG. 1 is a schematic of an embodiment of contacting system 100 used toproduce the total product as a vapor. The feed exits feed supply 101 andenters contacting zone 102 via conduit 104. A quantity of the catalystused in the contacting zone may range from about 1 gram to 1000 grams,about 2 grams to 500 grams, about 3 grams to 200 grams, about 4 grams to100 grams, about 5 grams to 50 grams, about 6 grams to 80 grams, about 7grams to 70 grams, or about 8 grams to 60 grams, per 100 grams of feedin the contacting zone. In some embodiments, contacting zone 102includes one or more fluidized bed reactors, one or more fixed bedreactors, or combinations thereof.

In certain embodiments, a diluent may be added to the feed to lower theviscosity of the feed. In some embodiments, the feed enters a bottomportion of contacting zone 102 via conduit 104. In certain embodiments,the feed may be heated to a temperature of at least 100° C. or at least300° C. prior to and/or during introduction of the feed to contactingzone 102. Typically, the feed may be heated to a temperature in a rangefrom about 100-500° C. or about 200-400° C.

In some embodiments, the catalyst is combined with the feed andtransferred to contacting zone 102. The feed/catalyst mixture may beheated to a temperature of at least 100° C. or at least 300° C. prior tointroduction into contacting zone 102. Typically, the feed may be heatedto a temperature in a range from about 200-500° C. or about 300-400° C.In some embodiments, the feed/catalyst mixture is a slurry. In certainembodiments, TAN of the feed may be reduced prior to introduction of thefeed into the contacting zone. For example, when the feed/catalystmixture is heated at a temperature in a range from about 100-400° C. orabout 200-300° C., alkali salts of acidic components in the feed may beformed. The formation of these alkali salts may remove some acidiccomponents from the feed to reduce the TAN of the feed.

In some embodiments, the feed is added continuously to contacting zone102. Mixing in contacting zone 102 may be sufficient to inhibitseparation of the catalyst from the feed/catalyst mixture. In certainembodiments, at least a portion of the catalyst may be removed fromcontacting zone 102, and in some embodiments, such catalyst isregenerated and re-used. In certain embodiments, fresh catalyst may beadded to contacting zone 102 during the reaction process.

In some embodiments, the feed and/or a mixture of feed with theinorganic salt catalyst is introduced into the contacting zone as anemulsion. The emulsion may be prepared by combining an inorganic saltcatalyst/water mixture with a feed/surfactant mixture. In someembodiments, a stabilizer is added to the emulsion. The emulsion mayremain stable for at least 2 days, at least 4 days, or at least 7 days.Typically, the emulsion may remain stable for 30 days, 10 days, 5 days,or 3 days. Surfactants include, but are not limited to, organicpolycarboxylic acids (Tenax 2010; MeadWestvaco Specialty Product Group;Charleston, S.C., U.S.A.), C₂₁ dicarboxylic fatty acid (DIACID 1550;MeadWestvaco Specialty Product Group), petroleum sulfonates (HostapurSAS 30; Clarient Corporation, Charlotte, N.C., U.S.A.), Tergital NP-40Surfactant (Union Carbide; Danbury, Conn., U.S.A.), or mixtures thereof.Stabilizers include, but are not limited to, diethyleneamine (AldrichChemical Co.; Milwaukee, Wis., U.S.A.) and/or monoethanolamine (J. T.Baker; Phillipsburg, N.J., U.S.A.).

Recycle conduit 106 may couple conduit 108 and conduit 104. In someembodiments, recycle conduit 106 may directly enter and/or exitcontacting zone 102. Recycle conduit 106 may include flow control valve110. Flow control valve 110 may allow at least a portion of the materialfrom conduit 108 to be recycled to conduit 104 and/or contacting zone102. In some embodiments, a condensing unit may be positioned in conduit108 to allow at least a portion of the material to be condensed andrecycled to contacting zone 102. In certain embodiments, recycle conduit106 may be a gas recycle line. Flow control valves 110 and 110′ may beused to control flow to and from contacting zone 102 such that aconstant volume of liquid in the contacting zone is maintained. In someembodiments, a substantially selected volume range of liquid can bemaintained in the contacting zone 102. A volume of feed in contactingzone 102 may be monitored using standard instrumentation. Gas inlet port112 may be used to allow addition of the hydrogen source and/oradditional gases to the feed as the feed enters contacting zone 102. Insome embodiments, steam inlet port 114 may be used to allow addition ofsteam to contacting zone 102. In certain embodiments, an aqueous streamis introduced into contacting zone 102 through steam inlet port 114.

In some embodiments, at least a portion of the total product is producedas vapor from contacting zone 102. In certain embodiments, the totalproduct is produced as vapor and/or a vapor containing small amounts ofliquids and solids from the top of contacting zone 102. The vapor istransported to separation zone 116 via conduit 108. The ratio of ahydrogen source to feed in contacting zone 102 and/or the pressure inthe contacting zone may be changed to control the vapor and/or liquidphase produced from the top of contacting zone 102. In some embodiments,the vapor produced from the top of contacting zone 102 includes at least0.5 grams, at least 0.8 grams, at least 0.9 grams, or at least 0.97grams of crude product per gram of feed. In certain embodiments, thevapor produced from the top of contacting zone 102 includes from about0.8-0.99 grams, or about 0.9-0.98 grams of crude product per gram offeed.

Used catalyst and/or solids may remain in contacting zone 102 asby-products of the contacting process. The solids and/or used catalystmay include residual feed and/or coke.

In separation unit 116, the vapor is cooled and separated to form thecrude product and gases using standard separation techniques. The crudeproduct exits separation unit 116 and enters crude product receiver 119via conduit 118. The resulting crude product may be suitable fortransportation and/or treatment. Crude product receiver 119 may includeone or more pipelines, one or more storage units, one or moretransportation vessels, or combinations thereof. In some embodiments,the separated gas (for example, hydrogen, carbon monoxide, carbondioxide, hydrogen sulfide, or methane) is transported to otherprocessing units (for example, for use in a fuel cell or a sulfurrecovery plant) and/or recycled to contacting zone 102 via conduit 120.In certain embodiments, entrained solids and/or liquids in the crudeproduct may be removed using standard physical separation methods (forexample, filtration, centrifugation, or membrane separation).

FIG. 2 depicts contacting system 122 for treating feed with one or morecatalysts to produce a total product that may be a liquid, or a liquidmixed with gas or solids. The feed may enter contacting zone 102 asdescribed herein via conduit 104. In some embodiments, the feed isreceived from the feed supply. Conduit 104 may include gas inlet port112. In some embodiments, gas inlet port 112 may directly entercontacting zone 102. In certain embodiments, steam inlet port 114 may beused to allow addition of the steam to contacting zone 102. The feed maybe contacted with the catalyst in contacting zone 102 to produce a totalproduct.

In some embodiments, conduit 106 allows at least a portion of the totalproduct to be recycled to contacting zone 102. A mixture that includesthe total product and/or solids and/or unreacted feed exits contactingzone 102 and enters separation zone 124 via conduit 108. In someembodiments, a condensing unit may be positioned (for example, inconduit 106) to allow at least a portion of the mixture in the conduitto be condensed and recycled to contacting zone 102 for furtherprocessing. In certain embodiments, recycle conduit 106 may be a gasrecycle line. In some embodiments, conduit 108 may include a filter forremoving particles from the total product.

In separation zone 124, at least a portion of the crude product may beseparated from the total product and/or catalyst. In embodiments inwhich the total product includes solids, the solids may be separatedfrom the total product using standard solid separation techniques (forexample, centrifugation, filtration, decantation, membrane separation).Solids include, for example, a combination of catalyst, used catalyst,and/or coke. In some embodiments, a portion of the gases is separatedfrom the total product. In some embodiments, at least a portion of thetotal product and/or solids may be recycled to conduit 104 and/or, insome embodiments, to contacting zone 102 via conduit 126. The recycledportion may, for example, be combined with the feed and enter contactingzone 102 for further processing. The crude product may exit separationzone 124 via conduit 128. In certain embodiments, the crude product maybe transported to the crude product receiver.

In some embodiments, contact of a catalyst with gas and a feed may beperformed under fluidization conditions. Fluidization of the catalystmay allow operation of the reaction to be preformed at less stringentconditions. For example, fluidization of the catalyst may lower thetotal amount of heat required to produce the total product, thus thecontacting zone may be operated at reduced temperatures and pressuresrelative to a slurry or fixed bed process. For example, catalyticcracking and steam reformation processes may be performed attemperatures of at most 1000° C., at most 900° C., at most 800° C., atmost 700° C., or at most 600° C. and at pressures of at most 4 MPa, atmost 3.5 MPa, at most, 3 MPa, or at most 2 MPa when using a supportedinorganic salt catalyst in a fluidized catalyst contacting zone.Fluidization of the catalyst may also allow an increased surface area ofcontact for the feed with the catalyst. An increased surface area ofcontact may lead to increased conversion of feed to total products.Additionally, coke production may be minimized at elevated temperatureswhen the process is conducted under fluidization conditions (forexample, at temperatures of at least 500° C., at least 700° C., at least800° C.). In some embodiments, an inorganic salt catalyst is a supportedcatalyst. Supported inorganic salt catalysts may be more readilyfluidized than unsupported inorganic salt catalysts.

FIG. 3 depicts contacting system 130 for treating a feed with one ormore catalysts to produce a total product that may be gas and/or liquid.Contacting zone 102 may be a fluidized reactor. The feed may entercontacting zone 102 via conduit 104. The feed may be heated aspreviously described, emulsified, and/or mixed with catalyst aspreviously described. Conduit 104 may include gas inlet port 112 andsteam inlet port 114. Steam inlet ports 114′, 114″ may directly entercontacting zone 102. In some embodiments, gas inlet port 112 maydirectly enter contacting zone 102. In certain embodiments, steam inletports 114′ and 114″ are not necessary. The catalyst may enter contactingzone via conduit 132. A quantity of the catalyst used in the contactingzone may range from about 1 gram to 1000 grams, about 2 grams to 500grams, about 3 grams to 200 grams, about 4 grams to 100 grams, about 5grams to 50 grams, about 6 grams to 80 grams, about 7 grams to 70 grams,or about 8 grams to 60 grams, per 100 grams of feed in the contactingzone. In some embodiments, the catalyst may enter contacting zone atvarious elevations of the contacting zone (for example, bottomelevation, middle elevation, and/or upper elevation). Conduit 106 allowsat least a portion of the total product/feed mixture to be recycled.

The catalyst may be fluidized through the upward lift of gas and feedand/or recycled total product/feed mixture, which are distributed acrossthe contacting zone through distributor 134 and a grid plate 136. Spentcatalyst and/or a portion of the total product/feed mixture may exitcontacting zone 102 via conduit 138. Pump 140 controls the flow offluidized liquid obtained from internal vapor/liquid separator 142. Theheight of the fluidized bed is adjusted by varying the speed of pump 140using methods known in the art.

In some embodiments, during contacting impurities (for example, coke,nitrogen containing compounds, sulfur containing compounds, and/ormetals such as nickel and/or vanadium) form on the catalyst. Removal ofthe impurities in situ may enhance contacting run times as compared toending the run and removing all the catalyst from the contacting zone.In situ removal of the impurities may be performed through combustion ofthe catalyst. In some embodiments, an oxygen source (for example, airand/or oxygen) may be introduced into contacting zone 102 to allowcombustion of impurities on the catalyst to occur. An oxygen source maybe added at a rate sufficient to from a combustion front, but the formedcombustion front is inhibited from entering the headspace of contactingzone 102 (for example, oxygen may be added at a rate sufficient tomaintain the total mole percent of oxygen in the head-space below 7percent). Heat from the combustion process may lessen the requirementfor heat from an external source to be added to contacting zone 102during use.

Feed may be fluidly contacted with hydrogen in the presence of one ormore catalysts in contacting zone 102 to produce a total product. Totalproduct may exit contacting zone 102 via conduit 108 and enterseparation zone 144. Separation zone may be similar, or the same as,previously described separation zones or separation zones know in theart. Total product may include crude product, gas, water, solids,catalyst, or combinations thereof. Temperatures in contacting zone 102may range from about 300° C. to about 1000° C., about 400° C. to about900° C., from about 500° C. to about 800° C., about 600° C. to about700° C. or about 750° C.

In separation zone 144, the total product is separated to form crudeproduct and/or gas. Crude product may exit separation zone 144 viaconduit 146. Gas may exit separation zone 144 via conduit 148. The crudeproduct and/or gas may be used as is or further processed. In someembodiments, separated catalyst may be regenerated and/or combined withfresh catalyst entering contacting zone 102.

Fluidly contacting the feed with a hydrogen source in the presence ofone or more inorganic metal salt catalysts may be an endothermicprocess. In some embodiments, fluidly contacting a feed with theinorganic metal salt catalyst may be up to 4 times as endothermic as aconventional fluidized catalytic cracking process. To provide sufficientheat transfer, an external heat source may be used to supply heat to thecontacting zone. The external heat supply may be a combustor, a catalystregeneration zone, a power plant, or any source of heat known in theart.

FIG. 4 depicts contacting system 150. Contacting system 150 may be afluidized catalytic cracking system and/or a modified fluidizedcatalytic cracking system. Contacting system 150 includes contactingzone 102, regeneration zone 152, and recovery zone 154. In someembodiments, contacting zone 102 and regeneration zone 152 are combinedas one zone. Contacting zone 102 includes fluidizer 156 and internalseparators 158, 158′. Feed enters contacting zone 102 via conduit 104.Catalyst enters contacting zone 102 via inlet port 160. A quantity ofthe catalyst used in the contacting zone may range from about 1-1000grams, about 2-500 grams, about 3-200 grams, about 4-100 grams, about5-50 grams, about 6-80 grams, about 7-70 grams, or about 8-60 grams, per100 grams of feed in the contacting zone. Conduit 104 may includecatalyst inlet port 160, gas inlet port 112, and steam inlet port 114.In some embodiments, steam, gas, and/or a hydrogen source may be mixedwith the feed and catalyst prior to entering contacting zone 102.

In some embodiments, contacting zone 102 may include steam inlet port114′. Steam inlet port 114′ may allow additional steam or superheatedsteam to be added to the contacting zone. Heat from the steam may allowmore controlled heating of the fluidizer 156. Fluidization of the feedand catalyst in fluidizer 156 may be performed using atomizationnozzles, spray nozzles, pumps, and/or other fluidizing methods known inthe art. In some embodiments, an oxygen source may be added tocontacting zone 102 as described for contacting system 130.

Internal separators 158, 158′ may separate a portion of the catalystfrom the total product/feed mixture and recycle the total product/feedmixture to fluidizer 156. Separated catalyst may exit contacting zone102 via conduit 162. Separated catalyst refers to used catalyst and/or amixture of used catalyst and new catalyst. Used catalyst refers tocatalyst that has been contacted with feed in the contacting zone.

Separated catalyst may enter regeneration zone 152 via conduit 166.Valve 164 may regulate flow of separated catalyst as it entersregeneration zone 152. An oxygen source may enter regeneration zone 152via gas inlet port 168. At least a portion of the catalyst may beregenerated by removal of impurities from the catalyst throughcombustion. During combustion, combustion gas (flue gas) and regeneratedcatalyst are formed. Heat generated from the combustion process may betransferred to contacting zone 102. Transferred heat may range fromabout 500° C. to about 1000° C., from about 600° C. to about 900° C., orfrom about 700° C. to about 800° C.

At least a portion of regenerated catalyst may exit regeneration zone152 via conduit 170. Valve 172 may be used to regulate flow of catalystinto conduit 104. In some embodiments, new catalyst and/or spenthydroprocessing catalyst is added to conduit 170 via conduit 174. Newcatalyst and/or spent hydroprocessing catalyst may be combined withregenerated catalyst in conduit 170. In some embodiments, the catalystis added to conduit 170 and/or contacting zone 102 using a sprayer.

Combustion gas may exit regeneration zone 152 and enter recovery zone154 via conduit 178. Combustion gas may include entrained inorganicsalts of the catalyst. In some embodiments, the combustion gas mayinclude catalyst particles, which may be removed using physicalseparation methods. In recovery zone 154, the combustion gas isseparated from catalyst and/or the inorganic salts. In some embodiments,the combustion gas includes a fluidized bed with particles that maycombine with the inorganic salts of the catalyst. The combinedparticle/inorganic salts may be separated from the combustion gas. Theseparated particle/inorganic salts may be used as and/or combined withthe catalyst entering contacting zone 102.

In some embodiments, the combustion gas may be treated with water topartially dissolve inorganic salts entrained in the combustion gas toform an aqueous inorganic salt solution. The aqueous inorganic saltsolution may be separated from the combustion gas using gas/liquidseparation methods known in the art. The aqueous inorganic salt solutionmay be heated to remove the water to form an inorganic salt catalystand/or recover the inorganic salts (for example, recover cesium,magnesium, calcium, and/or potassium salts). The recovered inorganicsalts and/or formed catalyst may be used as and/or combined with thecatalyst entering contacting zone 102. In some embodiments, therecovered inorganic salts may be sprayed into contacting zone 102 and/orconduit 174. In some embodiments, the recovered inorganic salts may bedeposited on a catalyst support and the result supported inorganic saltsmay enter and/or be sprayed into contacting zone 102 and/or conduit 174.

Contact of the feed with a hydrogen source in the presence of one ormore catalysts and steam in contacting system 150 produces a totalproduct. The total product may exit from an upper elevation ofcontacting zone via conduit 108. The total product enters separationzone 144 and is separated into crude product and/or gas. Crude productmay exit separation zone 144 via conduit 146. Gas may exit separationzone 144 via conduit 148. The crude product and/or gas may be used as isor further processed.

In some embodiments, the total product and/or crude product may includeat least a portion of the catalyst. Gases entrained in the total productand/or crude product may be separated using standard gas/liquidseparation techniques, for example, sparging, membrane separation, andpressure reduction. In some embodiments, the separated gas istransported to other processing units (for example, for use in a fuelcell, a sulfur recovery plant, other processing units, or combinationsthereof) and/or recycled to the contacting zone.

In some embodiments, separation of at least a portion of a feed isperformed before the feed enters the contacting zone. FIG. 5 is aschematic of an embodiment of a separation zone in combination with acontacting system. Contacting system 190 may be contacting system 100,contacting system 122, contacting system 130, contacting system 150, orcombinations thereof (shown in FIGS. 1 through 4). The feed entersseparation zone 192 via conduit 104. In separation zone 192, at least aportion of the feed is separated using standard separation techniques toproduce a separated feed and hydrocarbons. The separated feed, in someembodiments, includes a mixture of components with a boiling rangedistribution of at least 100° C., at least 120° C. or, in someembodiments, a boiling range distribution of at least 200° C. Typically,the separated feed includes a mixture of components with a boiling rangedistribution between about 100-1000° C., about 120-900° C., or about200-800° C. In some embodiments, the separated feed is VGO. Thehydrocarbons separated from the feed exit separation zone 192 viaconduit 194 to be transported to other processing units, treatmentfacilities, storage facilities, or combinations thereof.

At least a portion of the separated feed exits separation zone 192 andenters contacting system 190 via conduit 196 to be further processed toform the crude product, which exits contacting system 130 via conduit198.

In some embodiments, the crude product produced from a feed by anymethod described herein is blended with a crude that is the same as ordifferent from the feed. For example, the crude product may be combinedwith a crude having a different viscosity thereby resulting in a blendedproduct having a viscosity that is between the viscosity of the crudeproduct and the viscosity of the crude. The resulting blended productmay be suitable for transportation and/or treatment.

FIG. 6 is a schematic of an embodiment of a combination of blending zone200 and contacting system 190. In certain embodiments, at least aportion of the crude product exits contacting system 190 via conduit 198and enters blending zone 200. In blending zone 200, at least a portionof the crude product is combined with one or more process streams (forexample, a hydrocarbon stream produced from separation of one or morefeeds, or naphtha), a crude, a feed, or mixtures thereof, to produce ablended product. The process streams, feed, crude, or mixtures thereof,are introduced directly into blending zone 200 or upstream of theblending zone via conduit 202. A mixing system may be located in or nearblending zone 200. The blended product may meet specific productspecifications. Specific product specifications include, but are notlimited to, a range of or a limit of API gravity, TAN, viscosity, orcombinations thereof. The blended product exits blending zone 200 viaconduit 204 to be transported and/or processed.

In some embodiments, methanol is generated during the contacting processusing the catalyst. For example, hydrogen and carbon monoxide may reactto form methanol. The recovered methanol may contain dissolved salts,for example, potassium hydroxide. The recovered methanol may be combinedwith additional feed to form a feed/methanol mixture. Combining methanolwith the feed tends to lower the viscosity of the feed. Heating thefeed/methanol mixture to at most 500° C. may reduce TAN of the feed toless than 1.

FIG. 7 is a schematic of an embodiment of a separation zone incombination with a contacting system in combination with a blendingzone. The feed enters separation zone 192 through conduit 104. The feedis separated as previously described to form a separated feed. Theseparated feed enters contacting system 190 through conduit 196. Thecrude product exits contacting system 190 and enters blending zone 200through conduit 198. In blending zone 200, other process stream and/orcrudes introduced via conduit 202 are combined with the crude product toform a blended product. The blended product exits blending zone 200 viaconduit 204.

FIG. 8 is a schematic of multiple contacting system 206. Contactingsystem 208 (for example, contacting systems shown in FIGS. 1 through 4)may be positioned before contacting system 210. In an alternateembodiment, the positions of the contacting systems can be reversed.Contacting system 208 includes an inorganic salt catalyst. Contactingsystem 210 may include one or more catalysts. The catalyst in contactingsystem 210 may be an additional inorganic salt catalyst and/orcommercial catalysts. The feed enters contacting system 208 via conduit104 and is contacted with a hydrogen source in the presence of theinorganic salt catalyst to produce the total product. The total productincludes hydrogen and, in some embodiments, a crude product. The totalproduct may exit contacting system 208 via conduit 108. The hydrogengenerated from contact of the inorganic salt catalyst with the feed maybe used as a hydrogen source for contacting system 210. At least aportion of the generated hydrogen is transferred to contacting system210 from contacting system 208 via conduit 212.

In an alternate embodiment, such generated hydrogen may be separatedand/or treated, and then transferred to contacting system 210 viaconduit 212. In certain embodiments, contacting system 210 may be a partof contacting system 208 such that the generated hydrogen flows directlyfrom contacting system 208 to contacting system 210. In someembodiments, a vapor stream produced from contacting system 208 isdirectly mixed with the feed entering contacting system 210.

A second feed enters contacting system 210 via conduit 214. Incontacting system 210, contact of the feed with at least a portion ofthe generated hydrogen and the catalyst produces a product. The productis, in some embodiments, the total product. The product exits contactingsystem 210 via conduit 216.

In certain embodiments, a system that includes contacting systems,contacting zones, separation zones, and/or blending zones, as shown inFIGS. 1-8, may be located at or proximate to a production site thatproduces disadvantaged feed. After processing through the catalyticsystem, the feed and/or crude product may be considered suitable fortransportation and/or for use in a refinery process.

In some embodiments, the crude product and/or the blended product aretransported to a refinery and/or a treatment facility. The crude productand/or the blended product may be processed to produce commercialproducts such as transportation fuel, heating fuel, lubricants, orchemicals. Processing may include distilling and/or fractionallydistilling the crude product and/or blended product to produce one ormore distillate fractions. In some embodiments, the crude product, theblended product, and/or the one or more distillate fractions may behydrotreated.

The total product includes, in some embodiments, at most 0.2 grams ofcoke, at most 0.1 grams of coke, at most 0.05 grams, at most 0.03 grams,or at most 0.01 grams of coke per gram of total product. In certainembodiments, the total product is substantially free of coke (that is,coke is not detectable). In some embodiments, the crude product mayinclude at most 0.05 grams, at most 0.03 grams, at most 0.01 grams, atmost 0.005 grams, or at most 0.003 grams of coke per gram of crudeproduct. In certain embodiments, the crude product has a coke content ina range from above 0 to about 0.05, about 0.00001-0.03 grams, about0.0001-0.01 grams, or about 0.001-0.005 grams per gram of crude product,or is not detectable.

In certain embodiments, the crude product has an MCR content that is atmost 90%, at most 80%, at most 50%, at most 30%, or at most 10% of theMCR content of the feed. In some embodiments, the crude product has anegligible MCR content. In some embodiments, the crude product has, pergram of crude product, at most 0.05 grams, at most 0.03 grams, at most0.01 grams, or at most 0.001 grams of MCR. Typically, the crude producthas from about 0 grams to about 0.04 grams, about 0.000001-0.03 grams,or about 0.00001-0.01 grams of MCR per gram of crude product.

In some embodiments, the total product includes non-condensable gas. Thenon-condensable gas typically includes, but is not limited to, carbondioxide, ammonia, hydrogen sulfide, hydrogen, carbon monoxide, methane,other hydrocarbons that are not condensable at STP, or a mixturethereof.

In certain embodiments, hydrogen gas, carbon dioxide, carbon monoxide,or combinations thereof can be formed in situ by contact of steam, lighthydrocarbons, and feed with the inorganic salt catalyst. Certainembodiments of this kind of process are generally referred to as steamreforming. Reaction of feed, steam, hydrogen, and an inorganic saltcatalyst may occur under circulating fluidization conditions. Theinorganic salt catalysts used may include supported and non-supportedinorganic salt catalysts.

In some embodiments, an inorganic salt catalyst may be selected toproduce mostly gas or mostly crude product. For example, an inorganicsalt catalyst that is an alkaline-earth metal oxide may be selected toproduce gas and a minimal amount of crude product from a feed. Theproduced gas may include an enhanced amount of carbon oxides. Aninorganic salt catalyst that is a mixture of carbonates may be selectedto produce mostly crude product and a minimal amount of gas (e.g., in acatalytic cracking process). In some embodiments, a supported inorganicsalt catalyst may be used in a fluidized catalytic cracking process.

The total amount of carbon monoxide and carbon dioxide produced may beat least 0.1 grams, at least 0.3 grams, at least 0.5 grams, at least 0.8grams, at least 0.9 grams per gram of gas. The total amount of carbonmonoxide and carbon dioxide produce may range from about 0.1 grams to0.99 grams, about 0.2 grams to about 0.9 grams, about 0.3 grams to about0.8 grams or about 0.4 grams to about 0.7 grams per gram of gas. A molarratio of the generated carbon monoxide to the generated carbon dioxide,in some embodiments, is at least 0.3, at least 0.5, at least 0.7, atleast 1, at least 1.5, at least 2, or at least 3. In some embodiments, amolar ratio of the generated carbon monoxide to the generated carbondioxide is in a range from about 1:4, about 2:3, about 3:2, or about4:1. The ability to generate carbon monoxide preferentially to carbondioxide in situ may be beneficial to other processes located in aproximate area or upstream of the process. For example, the generatedcarbon monoxide may be used as a reducing agent in treating hydrocarbonformations or used in other processes, for example, syngas processes.

In some embodiments, the total product as produced herein may includecrude product, hydrocarbon gases, and carbon oxide gases (carbonmonoxide and carbon dioxide). A conversion of feed, based on molaramount of carbon in the feed, to total hydrocarbons (combined crudeproduct and hydrocarbon gases) produced may be at most 50%, at most 40%,at most 30, at most 20%, at most 10%, at most 1%. A conversion of feed,based on molar amount of carbon in the feed, to hydrocarbons producedmay range from 0 to about 50%, about 0.1% to about 40%, about 1% toabout 30%, about 5% to about 20% or about 3% to about 10%.

A conversion of feed, based on molar amount of carbon in the feed, tototal carbon oxide gases (combined carbon monoxide and carbon dioxide)produced may be at least 1%, at least 10%, at least 20%, at least 50%,at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%.A conversion of feed, based on molar amount of carbon in the feed, tohydrocarbons produce may range from 0 to about 99%, about 1% to about90%, about 5% to about 80%, about 10% to about 70%, about 20% to about60%, about 30% to about 50%.

In some embodiments, a content of hydrogen in the total product is lessthan a content of hydrogen in feed, based on molar amount of hydrogen inthe feed. A decreased amount of hydrogen in the total product may resultin products that differ from products produced using conventionalcracking, hydrotreating, and/or hydroprocessing methods.

In some embodiments, the total product as produced herein may include amixture of compounds that have a boiling range distribution betweenabout −10° C. and about 538° C. The mixture may include hydrocarbonsthat have carbon numbers in a range from 1 to 4. The mixture may includefrom about 0.001-0.8 grams, about 0.003-0.1 grams, or about 0.005-0.01grams, of C₄ hydrocarbons per gram of such mixture. The C₄ hydrocarbonsmay include from about 0.001-0.8 grams, about 0.003-0.1 grams, or about0.005-0.01 grams of butadiene per gram of C₄ hydrocarbons. In someembodiments, iso-paraffins are produced relative to n-paraffins at aweight ratio of at most 1.5, at most 1.4, at most 1.0, at most 0.8, atmost 0.3, or at most 0.1. In certain embodiments, iso-paraffins areproduce relative to n-paraffins at a weight ratio in a range from about0.00001-1.5, about 0.0001-1.0, or about 0.001-0.1. The paraffins mayinclude iso-paraffins and/or n-paraffins.

In some embodiments, the total product and/or crude product may includeolefins and/or paraffins in ratios or amounts that are not generallyfound in crudes produced and/or retorted from a formation. The olefinsinclude a mixture of olefins with a terminal double bond (“alphaolefins”) and olefins with internal double bonds. In certainembodiments, the olefin content of the crude product is greater than theolefin content of the feed by a factor of about 2, about 10, about 50,about 100, or at least 200. In some embodiments, the olefin content ofthe crude product is greater than the olefin content of the feed by afactor of at most 1,000, at most 500, at most 300, or at most 250.

In certain embodiments, the hydrocarbons with a boiling rangedistribution between 20-400° C. have an olefins content in a range fromabout 0.00001-0.1 grams, about 0.0001-0.05 grams, or about 0.01-0.04grams per gram of hydrocarbons having a boiling range distribution in arange between 20-400° C.

In some embodiments, at least 0.001 grams, at least 0.005 grams, or atleast 0.01 grams of alpha olefins per gram of crude product may beproduced. In certain embodiments, the crude product has from about0.0001-0.5 grams, about 0.001-0.2 grams, or about 0.01-0.1 grams ofalpha olefins per gram of crude product. In certain embodiments, thehydrocarbons with a boiling range distribution between about 20-400° C.have an alpha olefins content in a range from about 0.0001-0.08 grams,about 0.001-0.05 grams, or about 0.01-0.04 grams per gram ofhydrocarbons with a boiling range distribution between about 20-400° C.

In some embodiments, the hydrocarbons with a boiling range distributionbetween 20-204° C. have a weight ratio of alpha olefins to internaldouble bond olefins of at least 0.7, at least 0.8, at least 0.9, atleast 1.0, at least 1.4, or at least 1.5. In some embodiments, thehydrocarbons with a boiling range distribution between 20-204° C. have aweight ratio of alpha olefins to internal double bond olefins in a rangefrom about 0.7-10, about 0.8-5, about 0.9-3, or about 1-2. A weightratio of alpha olefins to internal double bond olefins of the crudes andcommercial products is typically at most 0.5. The ability to produce anincreased amount of alpha olefins to olefins with internal double bondsmay facilitate the conversion of the crude product to commercialproducts.

In some embodiments, contact of a feed with a hydrogen source in thepresence of an inorganic salt catalyst may produce hydrocarbons with aboiling range distribution between 20-204° C. that include linearolefins. The linear olefins have cis and trans double bonds. A weightratio of linear olefins with trans double bonds to linear olefins withcis double bonds is at most 0.4, at most 1.0, or at most 1.4. In certainembodiments, the weight ratio of linear olefins with trans double bondsto linear olefins with cis double bonds is in a range from about0.001-1.4, about 0.01-1.0, or about 0.1-0.4.

In certain embodiments, hydrocarbons having a boiling range distributionin a range between 20-204° C. have a n-paraffins content of at least 0.1grams, at least 0.15 grams, at least 0.20 grams, or at least 0.30 gramsper gram of hydrocarbons having a boiling range distribution in a rangebetween 20-400° C. The n-paraffins content of such hydrocarbons, pergram of hydrocarbons, may be in a range from about 0.001-0.9 grams,about 0.1-0.8 grams, or about 0.2-0.5 grams. In some embodiments, suchhydrocarbons have a weight ratio of the iso-paraffins to the n-paraffinsof at most 1.5, at most 1.4, at most 1.0, at most 0.8, or at most 0.3.From the n-paraffins content in such hydrocarbons, the n-paraffinscontent of the crude product may be estimated to be in a range fromabout 0.001-0.9 grams, about 0.01-0.8 grams, or about 0.1-0.5 grams pergram of crude product.

In some embodiments, the crude product has a total Ni/V/Fe content of atmost 90%, at most 50%, at most 10%, at most 5%, or at most 3% of aNi/V/Fe content of the feed. In certain embodiments, the crude productincludes, per gram of crude product, at most 0.0001 grams, at most1×10⁻⁵ grams, or at most 1×10⁻⁶ grams of Ni/V/Fe. In certainembodiments, the crude product has, per gram of crude product, a totalNi/V/Fe content in a range from about 1×10⁻⁷ grams to about 5×10⁻⁵grams, about 3×10⁻⁷ grams to about 2×10⁻⁵ grams, or about 1×10⁻⁶ gramsto about 1×10⁻⁵ grams.

In some embodiments, the crude product has a TAN of at most 90%, at most50%, or at most 10% of the TAN of the feed. The crude product may, incertain embodiments, have a TAN of at most 1, at most 0.5, at most 0.1,or at most 0.05. In some embodiments, TAN of the crude product may be ina range from about 0.001 to about 0.5, about 0.01 to about 0.2, or about0.05 to about 0.1.

In certain embodiments, the API gravity of the crude product is at least10% higher, at least 50% higher, or at least 90% higher than the APIgravity of the feed. In certain embodiments, API gravity of the crudeproduct is between about 13-50, about 15-30, or about 16-20.

In some embodiments, the crude product has a total heteroatoms contentof at most 70%, at most 50%, or at most 30% of the total heteroatomscontent of the feed. In certain embodiments, the crude product has atotal heteroatoms content of at least 10%, at least 40%, or at least 60%of the total heteroatoms content of the feed.

The crude product may have a sulfur content of at most 90%, at most 70%,or at most 60% of a sulfur content of the feed. The sulfur content ofthe crude product, per gram of crude product, may be at most 0.02 grams,at most 0.008 grams, at most 0.005 grams, at most 0.004 grams, at most0.003 grams, or at most 0.001 grams. In certain embodiments, the crudeproduct has, per gram of crude product, a sulfur content in a range fromabout 0.0001-0.02 grams or about 0.005-0.01 grams.

In certain embodiments, the crude product may have a nitrogen content ofat most 90% or at most 80% of a nitrogen content of the feed. Thenitrogen content of the crude product, per gram of crude product, may beat most 0.004 grams, at most 0.003 grams, or at most 0.001 grams. Insome embodiments, the crude product has, per gram of crude product, anitrogen content in a range from about 0.0001-0.005 grams, or about0.001-0.003 grams.

In some embodiments, the crude product has, per gram of crude product,from about 0.05-0.2 grams, or about 0.09-0.15 grams of hydrogen. Theatomic H/C of the crude product may be at most 1.8, at most 1.7, at most1.6, at most 1.5, or at most 1.4. In some embodiments, the atomic H/C ofthe crude product is about 80-120%, or about 90-110% of the atomic H/Cof the feed. In other embodiments, the atomic H/C of the crude productis about 100-120% of the atomic H/C of the feed. A crude product atomicH/C within 20% of the feed atomic H/C indicates that uptake and/orconsumption of hydrogen in the process is minimal.

The crude product includes components with a range of boiling points. Insome embodiments, the crude product includes: at least 0.001 grams, orfrom about 0.001 to about 0.5 grams of hydrocarbons with a boiling rangedistribution of at most 200° C. or at most 204° C. at 0.101 MPa; atleast 0.001 grams, or from about 0.001 to about 0.5 grams ofhydrocarbons with a boiling range distribution between about 200° C. andabout 300° C. at 0.101 MPa; at least 0.001 grams, or from about 0.001 toabout 0.5 grams of hydrocarbons with a boiling range distributionbetween about 300° C. and about 400° C. at 0.101 MPa; and at least 0.001grams, or from about 0.001 to about 0.5 grams of hydrocarbons with aboiling range distribution between about 400° C. and about 538° C. at0.101 MPa. In some embodiments, the crude product includes, per gram ofcrude product, from about 0.001 grams to about 0.9 grams, from about0.005 grams to about 0.8 grams, from about 0.01 grams to about 0.7grams, or from about 0.1 gram to about 0.6 grams of hydrocarbons with aboiling range distribution between about 204° C. and 343° C.

In some embodiments, the crude product has, per gram of crude product, anaphtha content from about 0.00001-0.2 grams, about 0.0001-0.1 grams, orabout 0.001-0.05 grams. In certain embodiments, the crude product hasfrom 0.001-0.2 grams or 0.01-0.05 grams of naphtha. In some embodiments,the naphtha has at most 0.15 grams, at most 0.1 grams, or at most 0.05grams of olefins per gram of naphtha. The crude product has, in certainembodiments, from 0.00001-0.15 grams, 0.0001-0.1 grams, or 0.001-0.05grams of olefins per gram of crude product. In some embodiments, thenaphtha has, per gram of naphtha, a benzene content of at most 0.01grams, at most 0.005 grams, or at most 0.002 grams. In certainembodiments, the naphtha has a benzene content that is non-detectable,or in a range from about 1×10⁻⁷ grams to about 1×10⁻² grams, about1×10⁻⁶ grams to about 1×10⁻⁵ grams, about 5×10⁻⁶ grams to about 1×10⁻⁴grams. Compositions that contain benzene may be considered hazardous tohandle, thus a crude product that has a relatively low benzene contentmay not require special handling.

In certain embodiments, naphtha may include aromatic compounds. Aromaticcompounds may include monocyclic ring compounds and/or polycyclic ringcompounds. The monocyclic ring compounds may include, but are notlimited to, benzene, toluene, ortho-xylene, meta-xylene, para-xylene,ethyl benzene, 1-ethyl-3-methyl benzene; 1-ethyl-2-methyl benzene;1,2,3-trimethyl benzene; 1,3,5-trimethyl benzene; 1-methyl-3-propylbenzene; 1-methyl-2-propyl benzene; 2-ethyl-1,4-dimethyl benzene;2-ethyl-2,4-dimethyl benzene; 1,2,3,4-tetra-methyl benzene; ethyl,pentylmethyl benzene; 1,3 diethyl-2,4,5,6-tetramethyl benzene;tri-isopropyl-ortho-xylene; substituted congeners of benzene, toluene,ortho-xylene, meta-xylene, para-xylene, or mixtures thereof. Monocyclicaromatics are used in a variety of commercial products and/or sold asindividual components. The crude product produced as described hereintypically has an enhanced content of monocyclic aromatics.

In certain embodiments, the crude product has, per gram of crudeproduct, a toluene content from about 0.001-0.2 grams, about 0.05-0.15grams, or about 0.01-0.1 grams. The crude product has, per gram of crudeproduct, a meta-xylene content from about 0.001-0.1 grams, about0.005-0.09 grams, or about 0.05-0.08 grams. The crude product has, pergram of crude product, an ortho-xylene content from about 0.001-0.2grams, about 0.005-0.1 grams, or about 0.01-0.05 grams. The crudeproduct has, per gram of crude product, a para-xylene content from about0.001-0.09 grams, about 0.005-0.08 grams, or about 0.001-0.06 grams.

An increase in the aromatics content of naphtha tends to increase theoctane number of the naphtha. Crudes may be valued based on anestimation of a gasoline potential of the crudes. Gasoline potential mayinclude, but is not limited to, a calculated octane number for thenaphtha portion of the crudes. Crudes typically have calculated octanenumbers in a range of about 35-60. The octane number of gasoline tendsto reduce the requirement for additives that increase the octane numberof the gasoline. In certain embodiments, the crude product includesnaphtha that has an octane number of at least 60, at least 70, at least80, or at least 90. Typically, the octane number of the naphtha is in arange from about 60-99, about 70-98, or about 80-95.

In some embodiments, the crude product has a higher total aromaticscontent in hydrocarbons having a boiling range distribution between 204°C. and 500° C. (total “naphtha and kerosene”) relative to the totalaromatics content in the total naphtha and kerosene of the feed by atleast 5%, at least 10%, at least 50%, or at least 99%. Typically, thetotal aromatics content in the total naphtha and kerosene of feed isabout 8%, about 20%, about 75%, or about 100% greater than the totalaromatics content in the total naphtha and kerosene of the feed.

In some embodiments, the kerosene and naphtha may have a totalpolyaromatic compounds content in a range from about 0.00001-0.5 grams,about 0.0001-0.2 grams, or about 0.001-0.1 grams per gram of totalkerosene and naphtha.

The crude product has, per gram of crude product, a distillate contentin a range from about 0.0001-0.9 grams, from about 0.001-0.5 grams, fromabout 0.005-0.3 grams, or from about 0.01-0.2 grams. In someembodiments, a weight ratio of kerosene to diesel in the distillate, isin a range from about 1:4 to about 4:1, about 1:3 to about 3:1, or about2:5 to about 5:2.

In some embodiments, crude product has, per gram of crude product, atleast 0.001 grams, from above 0 to about 0.7 grams, about 0.001-0.5grams, or about 0.01-0.1 grams of kerosene. In certain embodiments, thecrude product has from 0.001-0.5 grams or 0.01-0.3 grams of kerosene. Insome embodiments, the kerosene has, per gram of kerosene, an aromaticscontent of at least 0.2 grams, at least 0.3 grams, or at least 0.4grams. In certain embodiments, the kerosene has, per gram of kerosene,an aromatics content in a range from about 0.1-0.5 grams, or from about0.2-0.4 grams.

In certain embodiments, a freezing point of the kerosene may be below−30° C., below −40° C., or below −50° C. An increase in the content ofaromatics of the kerosene portion of the crude product tends to increasethe density and reduce the freezing point of the kerosene portion of thecrude product. A crude product with a kerosene portion having a highdensity and low freezing point may be refined to produce aviationturbine fuel with the desirable properties of high density and lowfreezing point.

In certain embodiments, the crude product has, per gram of crudeproduct, a diesel content in a range from about 0.001-0.8 grams or fromabout 0.01-0.4 grams. In certain embodiments, the diesel has, per gramof diesel, an aromatics content of at least 0.1 grams, at least 0.3grams, or at least 0.5 grams. In some embodiments, the diesel has, pergram of diesel, an aromatics content in a range from about 0.1-1 grams,about 0.3-0.8 grams, or about 0.2-0.5 grams.

In some embodiments, the crude product has, per gram of crude product, aVGO content in a range from about 0.0001-0.99 grams, from about0.001-0.8 grams, or from about 0.1-0.3 grams. In certain embodiments,the VGO content in the crude product is in a range from 0.4-0.9 grams,or about 0.6-0.8 grams per gram of crude product. In certainembodiments, the VGO has, per gram of VGO, an aromatics content in arange from about 0.1-0.99 grams, about 0.3-0.8 grams, or about 0.5-0.6grams.

In some embodiments, the crude product has a residue content of at most70%, at most 50%, at most 30%, at most 10%, or at most 1% of the feed.In certain embodiments, the crude product has, per gram of crudeproduct, a residue content of at most 0.1 grams, at most 0.05 grams, atmost 0.03 grams, at most 0.02 grams, at most 0.01 grams, at most 0.005grams, or at most 0.001 grams. In some embodiments, the crude producthas, per gram of crude product, a residue content in a range from about0.000001-0.1 grams, about 0.00001-0.05 grams, about 0.001-0.03 grams, orabout 0.005-0.04 grams.

In some embodiments, the crude product may include at least a portion ofthe catalyst. In some embodiments, a crude product includes from greaterthan 0 grams, but less than 0.01 grams, about 0.000001-0.001 grams, orabout 0.00001-0.0001 grams of catalyst per gram of crude product. Thecatalyst may assist in stabilizing the crude product duringtransportation and/or treatment in processing facilities. The catalystmay inhibit corrosion, inhibit friction, and/or increase waterseparation abilities of the crude product. A crude product that includesat least a portion of the catalyst may be further processed to producelubricants and/or other commercial products.

The catalyst used for treatment of a feed in the presence of a hydrogensource to produce the total product may be a single catalyst or aplurality of catalysts. The catalysts of the application may first be acatalyst precursor that is converted to the catalyst in the contactingzone when hydrogen and/or a feed containing sulfur is contacted with thecatalyst precursor.

The catalysts used in contacting the feed with a hydrogen source toproduce the total product may assist in the reduction of the molecularweight of the feed. Not to be bound by theory, the catalyst incombination with the hydrogen source may reduce a molecular weight ofcomponents in the feed through the action of basic (Lewis basic orBrønsted-Lowry basic) and/or superbasic components in the catalyst.Examples of catalysts that may have Lewis base and/or Brønsted-Lowrybase properties include catalysts described herein.

In some embodiments, the catalyst is an inorganic salt catalyst. Theanion of the inorganic salt catalyst may include an inorganic compound,an organic compound, or mixtures thereof. The inorganic salt catalystincludes alkali metal carbonates, alkali metal hydroxides, alkali metalhydrides, alkali metal amides, alkali metal sulfides, alkali metalacetates, alkali metal oxalates, alkali metal formates, alkali metalpyruvates, alkaline-earth metal carbonates, alkaline-earth metalhydroxides, alkaline-earth metal hydrides, alkaline-earth metal amides,alkaline-earth metal sulfides, alkaline-earth metal acetates,alkaline-earth metal oxalates, alkaline-earth metal formates,alkaline-earth metal pyruvates, or mixtures thereof.

Inorganic salt catalysts include, but are not limited to, mixtures of:NaOH/RbOH/CsOH; KOH/RbOH/CsOH; NaOH/KOH/RbOH; NaOH/KOH/CsOH;K₂CO₃/Rb₂CO₃/Cs₂CO₃; Na₂O/K₂O/K₂CO₃; NaHCO₃/KHCO₃/Rb₂CO₃;LiHCO₃/KHCO₃/Rb₂CO₃; KOH/RbOH/CsOH mixed with a mixture ofK₂CO₃/Rb₂CO₃/Cs₂CO₃; K₂CO₃/CaCO₃; K₂CO₃/MgCO₃; Cs₂CO₃/CaCO₃; Cs₂CO₃/CaO;Na₂CO₃/Ca(OH)₂; KH/CsCO₃; KOCHO/CaO; CsOCHO/CaCO₃; CsOCHO/Ca(OCHO)₂;NaNH₂/K₂CO₃/Rb₂O; K₂CO₃/CaCO₃/Rb₂CO₃; K₂CO₃/CaCO₃/Cs₂CO₃;K₂CO₃/MgCO₃/Rb₂CO₃; K₂CO₃/MgCO₃/Cs₂CO₃; or Ca(OH)₂ mixed with a mixtureof K₂CO₃/Rb₂CO₃/Cs₂CO₃. In some embodiments, the inorganic salt catalystis limestone (CaCO₃) or dolomite (CaMg(CO₃)₂).

In some embodiments, the inorganic salt catalyst is a alkaline-earthmetal oxide or a combination of alkaline-metal oxides In someembodiments, the inorganic salt catalyst also includes alkaline-earthmetal oxides and/or oxides of metals from Column 13 of the PeriodicTable. Metals from Column 13 include, but are not limited to, boron oraluminum. Non-limiting examples of metal oxides include lithium oxide(Li₂O), potassium oxide (K₂O), calcium oxide (CaO), magnesium oxide(MgO), or aluminum oxide (Al₂O₃).

In certain embodiments, an inorganic salt catalyst includes one or morealkali metal salts that include an alkali metal with an atomic number ofat least 11. An atomic ratio of an alkali metal having an atomic numberof at least 11 to an alkali metal having an atomic number greater than11, in some embodiments, is in a range from about 0.1 to about 10, about0.2 to about 6, or about 0.3 to about 4 when the inorganic salt catalysthas two or more alkali metals. For example, the inorganic salt catalystmay include salts of sodium, potassium, and rubidium with the ratio ofsodium to potassium being in a range from about 0.1-6; the ratio ofsodium to rubidium being in a range from about 0.1-6; and the ratio ofpotassium to rubidium being in a range from about 0.1-6. In anotherexample, the inorganic salt catalyst includes a sodium salt and apotassium salt with the atomic ratio of sodium to potassium being in arange from about 0.1 to about 4.

In some embodiments, an inorganic salt catalyst also includes metalsfrom Columns 8-10 of the Periodic Table, compounds of metals fromColumns 8-10 of the Periodic Table, metals from Column 6 of the PeriodicTable, compounds of metals from Column 6 of the Periodic Table, ormixtures thereof. Metals from Columns 8-10 include, but are not limitedto, iron, ruthenium, cobalt, or nickel. Metals from Column 6 include,but are not limited to, chromium, molybdenum, or tungsten. In someembodiments, the inorganic salt catalyst includes about 0.1-0.5 grams,or about 0.2-0.4 grams of Raney nickel per gram of inorganic saltcatalyst.

In some embodiments, the inorganic salt catalyst contains at most0.00001 grams, at most 0.001 grams, or at most 0.01 grams of lithium,calculated as the weight of lithium, per gram of inorganic saltcatalyst. The inorganic salt catalyst has, in some embodiments, fromabout 0 but less than 0.01 grams, about 0.0000001-0.001 grams, or about0.00001-0.0001 grams of lithium, calculated as the weight of lithium,per gram of inorganic salt catalyst.

The inorganic salt catalyst is, in certain embodiments, free of orsubstantially free of Lewis acids (for example, BCl₃, AlCl₃, and SO₃),Brønsted-Lowry acids (for example, H₃O⁺, H₂SO₄, HCl, and HNO₃),glass-forming compositions (for example, borates and silicates), andhalides. The inorganic salt may contain, per gram of inorganic saltcatalyst: from about 0 grams to about 0.1 grams, about 0.000001-0.01grams, or about 0.00001-0.005 grams of: a) halides; b) compositions thatform glasses at temperatures of at least 350° C., or at most 1000° C.;c) Lewis acids; d) Brønsted-Lowry acids; or e) mixtures thereof.

The inorganic salt catalyst may be prepared using standard techniques.For example, a desired amount of each component of the catalyst may becombined using standard mixing techniques (for example, milling and/orpulverizing). In other embodiments, inorganic compositions are dissolvedin a solvent (for example, water or a suitable organic solvent) to forman inorganic composition/solvent mixture. The solvent may be removedusing standard separation techniques to produce the inorganic saltcatalyst.

In some embodiments, inorganic salts of the inorganic salt catalyst maybe incorporated into a support to form a supported inorganic saltcatalyst. The support, in some embodiments, exhibits chemical resistanceto the basicity of the inorganic salt at high temperatures. The supportmay have the ability to absorb heat (for example, have a high heatcapacity). The ability of the support of the inorganic salt catalyst toabsorb heat may allow temperatures in the contacting zone to be reducedas compared to the temperature of the contacting zone when anunsupported inorganic salt catalyst is used. Examples of supportsinclude, but are not limited to, zirconium oxide, calcium oxide,magnesium oxide, titanium oxide, hydrotalcite, germania, iron oxide,nickel oxide, zinc oxide, cadmium oxide, antimony oxide, calciummagnesium carbonate, aluminosilicate, limestone, dolomite, activatedcarbon, nonvolatile charcoal, and mixtures thereof. In some embodiments,an inorganic salt, a Columns 6-10 metal, and/or a compound of a Columns6-10 metal may be impregnated in the support. In certain embodiments,the compound of a Columns 6-10 metal is a metal sulfide (for example,nickel sulfide, vanadium sulfide, molybdenum sulfide, tungsten sulfide,iron sulfide). Alternatively, inorganic salts may be melted or softenedwith heat and forced in and/or onto a metal support or metal oxidesupport to form a supported inorganic salt catalyst. In someembodiments, a spent hydroprocessing catalyst is combined with theinorganic salt catalyst support and/or used with an inorganic saltcatalyst. In some embodiments, metals and/or compounds of metalsrecovered from a total product/feed mixture is combined the inorganicsalt catalyst support and/or used with an inorganic salt catalyst.

In some embodiments, an inorganic salt catalyst is mixed with a Column 4metal oxide. Column 4 metal oxides include, but are not limited to, ZrO₂and/or TiO₂. A molar ratio of inorganic salt catalyst to Column 4 metaloxide may range from about 0.01 to about 5, from about 0.5 to about 4,or from about 1 to about 3.

In some embodiments, the supported inorganic salt catalyst ischaracterized using particle size. The particle size of a supportedinorganic salt catalyst may range from about 20 micrometers to about 500micrometers, from about 30 micrometers to about 400 micrometers, fromabout 50 micrometers to about 300 micrometers, or from about 100 to 200micrometers.

In some embodiments, a structure of the inorganic salt catalysttypically becomes nonhomogenous, permeable, and/or mobile at adetermined temperature or in a temperature range when loss of orderoccurs in the catalyst structure. The inorganic salt catalyst may becomedisordered without a substantial change in composition (for example,without decomposition of the salt). Not to be bound by theory, it isbelieved that the inorganic salt catalyst becomes disordered (mobile)when distances between ions in the lattice of the inorganic saltcatalyst increase. As the ionic distances increase, a feed and/or ahydrogen source may permeate through the inorganic salt catalyst insteadof across the surface of the inorganic salt catalyst. Permeation of thefeed and/or hydrogen source through the inorganic salt often results inan increase in the contacting area between the inorganic salt catalystand the feed and/or the hydrogen source. An increase in contacting areaand/or reactivity area of the inorganic salt catalyst may often increasethe yield of crude product, limit production of residue and/or coke,and/or facilitate a change in properties in the crude product relativeto the same properties of the feed. Disorder of the inorganic saltcatalyst (for example, nonhomogeneity, permeability, and/or mobility)may be determined using DSC methods, ionic conductivity measurementmethods, TAP methods, visual inspection, x-ray diffraction methods, orcombinations thereof.

The use of TAP to determine characteristics of catalysts is described inU.S. Pat. No. 4,626,412 to Ebner et al.; U.S. Pat. No. 5,039,489 toGleaves et al.; and U.S. Pat. No. 5,264,183 to Ebner et al., all ofwhich are incorporated herein by reference. A TAP system may be obtainedfrom Mithra Technologies (Foley, Mo., U.S.A.). The TAP analysis may beperformed in a temperature range from about 25-850° C., about 50-500°C., or about 60-400° C., at a heating rate in a range from about 10-50°C., or about 20-40° C., and at a vacuum in a range from about 1×10⁻¹³ toabout 1×10⁻⁸ torr. The temperature may remain constant and/or increaseas a function of time. As the temperature of the inorganic salt catalystincreases, gas emission from the inorganic salt catalyst is measured.Examples of gases that evolve from the inorganic salt catalyst includecarbon monoxide, carbon dioxide, hydrogen, water, or mixtures thereof.The temperature at which an inflection (sharp increase) in gas evolutionfrom the inorganic salt catalyst is detected is considered to be thetemperature at which the inorganic salt catalyst becomes disordered.

In some embodiments, an inflection of emitted gas from the inorganicsalt catalyst may be detected over a range of temperatures as determinedusing TAP. The temperature or the temperature range is referred to asthe “TAP temperature”. The initial temperature of the temperature rangedetermined using TAP is referred to as the “minimum TAP temperature”.

The emitted gas inflection exhibited by inorganic salt catalystssuitable for contact with a feed is in a TAP temperature range fromabout 100-600° C., about 200-500° C., or about 300-400° C. Typically,the TAP temperature is in a range from about 300-500° C. In someembodiments, different compositions of suitable inorganic salt catalystsalso exhibit gas inflections, but at different TAP temperatures.

The magnitude of the ionization inflection associated with the emittedgas may be an indication of the order of the particles in a crystalstructure. In a highly ordered crystal structure, the ion particles aregenerally tightly associated, and release of ions, molecules, gases, orcombinations thereof, from the structure requires more energy (that ismore heat). In a disordered crystal structure, ions are not associatedto each other as strongly as ions in a highly ordered crystal structure.Due to the lower ion association, less energy is generally required torelease ions, molecules, and/or gases from a disordered crystalstructure, and thus, a quantity of ions and/or gas released from adisordered crystal structure is typically greater than a quantity ofions and/or gas released from a highly ordered crystal structure at aselected temperature.

In some embodiments, a heat of dissociation of the inorganic saltcatalyst may be observed in a range from about 50° C. to about 500° C.at a heating rate or cooling rate of about 10° C., as determined using adifferential scanning calorimeter. In a DSC method, a sample may beheated to a first temperature, cooled to room temperature, and thenheated a second time. Transitions observed during the first heatinggenerally are representative of entrained water and/or solvent and maynot be representative of the heat of dissociations. For example, easilyobserved heat of drying of a moist or hydrated sample may generallyoccur below 250° C., typically between 100-150° C. The transitionsobserved during the cooling cycle and the second heating correspond tothe heat of dissociation of the sample.

“Heat transition” refers to the process that occurs when orderedmolecules and/or atoms in a structure become disordered when thetemperature increases during the DSC analysis. “Cool transition” refersto the process that occurs when molecules and/or atoms in a structurebecome more homogeneous when the temperature decreases during the DSCanalysis. In some embodiments, the heat/cool transition of the inorganicsalt catalyst occurs over a range of temperatures that are detectedusing DSC. The temperature or temperature range at which the heattransition of the inorganic salt catalyst occurs during a second heatingcycle is referred to as “DSC temperature”. The lowest DSC temperature ofthe temperature range during a second heating cycle is referred to asthe “minimum DSC temperature”. The inorganic salt catalyst may exhibit aheat transition in a range between about 200-500° C., about 250-450° C.,or about 300-400° C.

In an inorganic salt that contains inorganic salt particles that are arelatively homogeneous mixture, a shape of the peak associated with theheat absorbed during a second heating cycle may be relatively narrow. Inan inorganic salt catalyst that contains inorganic salt particles in arelatively non-homogeneous mixture, the shape of the peak associatedwith heat absorbed during a second heating cycle may be relativelybroad. An absence of peaks in a DSC spectrum indicates that the saltdoes not absorb or release heat in the scanned temperature range. Lackof a heat transition generally indicates that the structure of thesample does not change upon heating.

As homogeneity of the particles of an inorganic salt mixture increases,the ability of the mixture to remain a solid and/or a semiliquid duringheating decreases. Homogeneity of an inorganic mixture may be related tothe ionic radius of the cations in the mixtures. For cations withsmaller ionic radii, the ability of a cation to share electron densitywith a corresponding anion increases and the acidity of thecorresponding anion increases. For a series of ions of similar charges,a smaller ionic radius results in higher interionic attractive forcesbetween the cation and the anion if the anion is a hard base. The higherinterionic attractive forces tend to result in higher heat transitiontemperatures for the salt and/or more homogeneous mixture of particlesin the salt (sharper peak and increased area under the DSC curve).Mixtures that include cations with small ionic radii tend to be moreacidic than cations of larger ionic radii, and thus acidity of theinorganic salt mixture increases with decreasing cationic radii. Forexample, contact of a feed with a hydrogen source in the presence of aninorganic mixture that includes lithium cations tends to produceincreased quantities of gas and/or coke relative to contact of the feedwith a hydrogen source in the presence of an inorganic salt catalystthat includes cations with a larger ionic radii than lithium. Theability to inhibit generation of gas and/or coke increases the totalliquid product yield of the process.

In certain embodiments, the inorganic salt catalyst may include two ormore inorganic salts. A minimum DSC temperature for each of theinorganic salts may be determined. The minimum DSC temperature of theinorganic salt catalyst may be below the minimum DSC temperature of atleast one of the inorganic metal salts in the inorganic salt catalyst.For example, the inorganic salt catalyst may include potassium carbonateand cesium carbonate. Potassium carbonate and cesium carbonate exhibitDSC temperatures greater than 500° C. A K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalystexhibits a DSC temperature in a range from about 290-300° C.

In some embodiments, the TAP temperature may be between the DSCtemperature of at least one of the inorganic salts and the DSCtemperature of the inorganic salt catalyst. For example, the TAPtemperature of the inorganic salt catalyst may be in a range from about350-500° C. The DSC temperature of the same inorganic salt catalyst maybe in a range from about 200-300° C., and the DSC temperature of theindividual salts may be at least 500° C. or at most 1000° C.

An inorganic salt catalyst that has a TAP and/or DSC temperature betweenabout 150-500° C., about 200-450° C., or about 300-400° C., and does notundergo decomposition at these temperatures, in many embodiments, can beused to catalyze conversion of high molecular weight and/or highviscosity compositions (for example, feed) to liquid products.

In certain embodiments, the inorganic salt catalyst may exhibitincreased conductivity relative to individual inorganic salts duringheating of the inorganic salt catalyst in a temperature range from about200-600° C., about 300-500° C., or about 350-450° C. Increasedconductivity of the inorganic salt catalyst is generally attributed tothe particles in the inorganic salt catalyst becoming mobile. The ionicconductivity of some inorganic salt catalysts changes at a lowertemperature than the temperature at which ionic conductivity of a singlecomponent of the inorganic salt catalyst changes.

Ionic conductivity of inorganic salts may be determined by applyingOhm's law: V=IR, where V is voltage, I is current, and R is resistance.To measure ionic conductivity, the inorganic salt catalyst may be placedin a quartz vessel with two wires (for example, copper wires or platinumwires) separated from each other, but immersed in the inorganic saltcatalyst.

FIG. 9 is a schematic of a system that may be used to measure ionicconductivity. Quartz vessel 220 containing sample 222 may be placed in aheating apparatus and heated incrementally to a desired temperature.Voltage from source 224 is applied to wire 226 during heating. Theresulting current through wires 226 and 228 is measured at meter 230.Meter 230 may be, but is not limited to, a multimeter or a Wheatstonebridge. As sample 222 becomes less homogeneous (more mobile) withoutdecomposition occurring, the resistivity of the sample should decreaseand the observed current at meter 230 should increase.

In some embodiments, at a desired temperature, the inorganic saltcatalyst may have a different ionic conductivity after heating, cooling,and then heating. The difference in ionic conductivities may indicatethat the crystal structure of the inorganic salt catalyst has beenaltered from an original shape (first form) to a different shape (secondform) during heating. The ionic conductivities, after heating, areexpected to be similar or the same if the form of the inorganic saltcatalyst does not change during heating.

In certain embodiments, the inorganic salt catalyst has a particle sizein a range of about 10-1000 micrometers, about 20-500 micrometers, orabout 50-100 micrometers, as determined by passing the inorganic saltcatalyst through a mesh or a sieve.

The inorganic salt catalyst may soften when heated to temperatures above50° C. and below 500° C. As the inorganic salt catalyst softens, liquidsand catalyst particles may co-exist in the matrix of the inorganic saltcatalyst. The catalyst particles may, in some embodiments, self-deformunder gravity, or under a pressure of at least 0.007 MPa, or at most0.101 MPa, when heated to a temperature of at least 300° C., or at most800° C., such that the inorganic salt catalyst transforms from a firstform to a second form. Upon cooling of the inorganic salt catalyst toabout 20° C., the second form of the inorganic salt catalyst isincapable of returning to the first form of the inorganic salt catalyst.The temperature at which the inorganic salt transforms from the firstform to a second form is referred to as the “deformation” temperature.The deformation temperature may be a temperature range or a singletemperature. In certain embodiments, the particles of the inorganic saltcatalyst self-deform under gravity or pressure upon heating to adeformation temperature below the deformation temperature of any of theindividual inorganic metal salts. In some embodiments, an inorganic saltcatalyst includes two or more inorganic salts that have differentdeformation temperatures. The deformation temperature of the inorganicsalt catalyst differs, in some embodiments, from the deformationtemperatures of the individual inorganic metal salts.

In certain embodiments, the inorganic salt catalyst is liquid and/orsemiliquid at, or above, the TAP and/or DSC temperature. In someembodiments, the inorganic salt catalyst is a liquid or a semiliquid atthe minimum TAP and/or DSC temperature. At or above the minimum TAPand/or DSC temperature, liquid or semiliquid inorganic salt catalystmixed with the feed may, in some embodiments, form a separate phase fromthe feed. In some embodiments, the liquid or semiliquid inorganic saltcatalyst has low solubility in the feed (for example, from about 0 gramsto about 0.5 grams, about 0.0000001-0.2 grams, or about 0.0001-0.1 gramsof inorganic salt catalyst per gram of feed) or is insoluble in the feed(for example, from about 0 grams to about 0.05 grams, about0.000001-0.01 grams, or about 0.00001-0.001 grams of inorganic saltcatalyst per gram of feed) at the minimum TAP temperature.

In some embodiments, powder x-ray diffraction methods are used todetermine the spacing of the atoms in the inorganic salt catalyst. Ashape of the D₀₀₁ peak in the x-ray spectrum may be monitored and therelative order of the inorganic salt particles may be estimated. Peaksin the x-ray diffraction represent different compounds of the inorganicsalt catalyst. In powder x-ray diffraction, the D₀₀₁ peak may bemonitored and the spacing between atoms may be estimated. In aninorganic salt catalyst that contains highly ordered inorganic saltatoms, a shape of the D₀₀₁ peak is relatively narrow. In an inorganicsalt catalyst (for example, a K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst) thatcontains randomly ordered inorganic salt atoms, the shape of the D₀₀₁peak may be relatively broad or the D₀₀₁ peak may be absent. Todetermine if the disorder of inorganic salt atoms changes duringheating, an x-ray diffraction spectrum of the inorganic salt catalystmay be taken before heating and compared with an x-ray diffractionspectrum taken after heating. The D₀₀₁ peak (corresponding to theinorganic salt atoms) in the x-ray diffraction spectrum taken attemperatures above 50° C. may be absent or broader than the D₀₀₁ peaksin the x-ray diffraction spectrum taken at temperatures below 50° C.Additionally, the x-ray diffraction pattern of the individual inorganicsalt may exhibit relatively narrow D₀₀₁ peaks at the same temperatures.

Contacting conditions may be controlled such that the total productcomposition (and thus, the crude product) may be varied for a given feedin addition to limiting and/or inhibiting formation of by-products. Thetotal product composition includes, but is not limited to, paraffins,olefins, aromatics, or mixtures thereof. These compounds make up thecompositions of the crude product and the non-condensable hydrocarbongases.

Controlling contacting conditions in combination with the catalystdescribed herein may produce a total product with lower than predictedcoke content. Comparison of the MCR content of various crudes may allowcrudes to be ranked based on their tendency to form coke. For example, acrude with a MCR content of about 0.1 grams of MCR per gram of crudewould be expected to form more coke than a crude with a MCR content ofabout 0.001 grams of MCR per gram of crude. Disadvantaged crudestypically have MCR contents of at least 0.05 grams of MCR per gram ofdisadvantaged crude.

In some embodiments, the residue content and/or coke content depositedon the catalyst during a reaction period may be at most 0.2 grams, atmost 0.1 grams, at most 0.05 grams, or at most 0.03 grams of residueand/or coke per gram of catalyst. In certain embodiments, the weight ofresidue and/or coke deposited on the catalyst is in a range from about0.0001-0.1 grams, 0.001-0.05 grams, or about 0.01-0.03 grams. In someembodiments, used catalyst is substantially free of residue and/or coke.In certain embodiments, contacting conditions are controlled such thatat most 0.2 grams, at most 0.1 grams, at most 0.05 grams, at most 0.015grams, at most 0.01 grams, at most 0.005 grams, or at most 0.003 gramsof coke is formed per gram of crude product. Contacting a feed with thecatalyst under controlled contacting conditions produces a reducedquantity of coke and/or residue relative to a quantity of coke and/orresidue produced by heating the feed in the presence of a refiningcatalyst, or in the absence of a catalyst, using the same contactingconditions.

The contacting conditions may be controlled, in some embodiments, suchthat, per gram of feed, at least 0.5 grams, at least 0.7 grams, at least0.8 grams, or at least 0.9 grams of the feed is converted to the crudeproduct. Typically, between about 0.5-0.99 grams, about 0.6-0.9 grams,or about 0.7-0.8 grams of the crude product per gram of feed is producedduring contacting. Conversion of the feed to a crude product with aminimal yield of residue and/or coke, if any, in the crude productallows the crude product to be converted to commercial products with aminimal amount of pre-treatment at a refinery. In certain embodiments,per gram of feed, at most 0.2 grams, at most 0.1 grams, at most 0.05grams, at most 0.03 grams, or at most 0.01 grams of the feed isconverted to non-condensable hydrocarbons. In some embodiments, fromabout 0 to about 0.2 grams, about 0.0001-0.1 grams, about 0.001-0.05grams, or about 0.01-0.03 grams of non-condensable hydrocarbons per gramof feed is produced.

Controlling a contacting zone temperature, rate of feed flow, rate oftotal product flow, rate and/or amount of catalyst feed, rate of steamflow, or combinations thereof, may be performed to maintain desiredreaction temperatures. In some embodiments, control of the temperaturein the contacting zone may be performed by changing a flow of a gaseoushydrogen source and/or inert gas through the contacting zone to dilutethe amount of hydrogen and/or remove excess heat from the contactingzone.

In some embodiments, the temperature in the contacting zone may becontrolled such that a temperature in the contacting zone is at, above,or below desired temperature “T₁”. In certain embodiments, thecontacting temperature is controlled such that the contacting zonetemperature is below the minimum TAP temperature and/or the minimum DSCtemperature. In certain embodiments, T₁ may be about 30° C. below, about20° C. below, or about 10° C. below the minimum TAP temperature and/orthe minimum DSC temperature. For example, in one embodiment, thecontacting temperature may be controlled to be about 370° C., about 380°C., or about 390° C. during the reaction period when the minimum TAPtemperature and/or minimum DSC temperature is about 400° C.

In other embodiments, the contacting temperature is controlled such thatthe temperature is at, or above, the catalyst TAP temperature and/or thecatalyst DSC temperature. For example, the contacting temperature may becontrolled to be about 450° C., about 500° C., or about 550° C. duringthe reaction period when the minimum TAP temperature and/or minimum DSCtemperature is about 450° C. Controlling the contacting temperaturebased on catalyst TAP temperatures and/or catalyst DSC temperatures mayyield improved crude product properties. Such control may, for example,decrease coke formation, decrease non-condensable gas formation, orcombinations thereof.

In certain embodiments, the inorganic salt catalyst may be conditionedprior to addition of the feed. In some embodiments, the conditioning maytake place in the presence of the feed. Conditioning the inorganic saltcatalyst may include heating the inorganic salt catalyst to a firsttemperature of at least 100° C., at least 300° C., at least 400° C., orat least 500° C., and then cooling the inorganic salt catalyst to asecond temperature of at most 250° C., at most 200° C., or at most 100°C. In certain embodiments, the inorganic salt catalyst is heated to atemperature in a range from about 150-700° C., about 200-600° C., orabout 300-500° C., and then cooled to a second temperature in a rangefrom about 25-240° C., about 30-200° C., or about 50-90° C. Theconditioning temperatures may be determined by determining ionicconductivity measurements at different temperatures. In someembodiments, conditioning temperatures may be determined from DSCtemperatures obtained from heat/cool transitions obtained by heating andcooling the inorganic salt catalyst multiple times in a DSC.Conditioning of the inorganic salt catalyst may allow contact of a feedto be performed at lower reaction temperatures than temperatures usedwith conventional hydroprocessing catalysts.

In certain embodiments, varying a ratio of catalyst to feed may affectthe amount of gas, crude product, and/or coke formed during contacting.A ratio supported inorganic catalyst to feed may range from 2-10 or begreater than 10. The conversion of feed to total product may be at least50%, at least 60%, at least 80%, at least 90%, at least 99%. The contentof gas in the total product may range be, per gram of feed, at least 0.1grams, at least 0.5 grams, at least 0.7 grams, at least 0.9 grams or atleast 0.95 grams. The content of produced product may range, per gram offeed, from about 0.1 grams to 0.99 grams, 0.3 grams to 0.9 grams, orfrom about 0.5 gram to about 0.7 grams. The content crude product in thetotal product may range be, per gram of feed, at least 0.1 grams, atleast 0.5 grams, at least 0.7 grams, at least 0.9 grams or at least 0.95grams. The content of produced crude product may range, per gram offeed, from about 0.1 grams to 0.99 grams, 0.3 grams to 0.9 grams, orfrom about 0.5 gram to about 0.7 grams. At most, per gram of feed, 0.2grams, at most 0.1 grams, at most 0.05 grams of coke may be formed.

In some embodiments, a content of naphtha, distillate, VGO, or mixturesthereof, in the total product, may be varied by changing a rate of totalproduct removal from a contacting zone. For example, decreasing a rateof total product removal tends to increase contacting time of the feedwith the catalyst. Alternately, increasing pressure relative to aninitial pressure may increase contacting time, may increase a yield of acrude product, may increase incorporation of hydrogen from the gasesinto a crude product for a given mass flow rate of feed or hydrogensource, or may alter combinations of these effects. Increased contactingtimes of the feed with the catalyst may produce an increased amount ofdiesel, kerosene, or naphtha and a decreased amount of VGO relative tothe amounts of diesel, kerosene, naphtha, and VGO produced at shortercontacting times. Increasing the contacting time of the total product inthe contacting zone may also change the average carbon number of thecrude product. Increased contacting time may result in a higher weightpercentage of lower carbon numbers (and thus, a higher API gravity).

In some embodiments, the contacting conditions may be changed over time.For example, the contacting pressure and/or the contacting temperaturemay be increased to increase the amount of hydrogen that the feeduptakes to produce the crude product. The ability to change the amountof hydrogen uptake of the feed, while improving other properties of thefeed, increases the types of crude products that may be produced from asingle feed. The ability to produce multiple crude products from asingle feed may allow different transportation and/or treatmentspecifications to be satisfied.

Contacting a feed with an inorganic salt catalyst in the presence oflight hydrocarbons and steam generates hydrogen and carbon monoxide insitu. The carbon monoxide reacts with more steam to produce carbondioxide and more hydrogen. The hydrogen may be incorporated into thefeed under basic conditions to form new products. Controlling the amountof steam, the temperature of the contacting zone, and selection ofcatalyst may produce hydrocarbons from the feed that differ fromhydrocarbons obtained from conventional catalytic cracking methods.

Uptake of hydrogen may be assessed by comparing the atomic H/C of thefeed to H/C of the crude product. An increase in the atomic H/C of thecrude product relative to the atomic H/C of the feed indicatesincorporation of hydrogen into the crude product from the hydrogensource. Relatively low increase in the atomic H/C of the crude product(about 20%, as compared to the feed) indicates relatively lowconsumption of hydrogen gas during the process. Significant improvementof the crude product properties, relative to those of the feed, obtainedwith minimal consumption of hydrogen is desirable.

Depending on the desired composition of the total product, the amount ofsteam may be varied. To produce a total product that has increasedamounts of gas relative to liquid, more steam may be added to thecontacting zone. A weight ratio of steam to feed may range from 0.001 to100 from 0.01 to 10, from 0.05 to 5, or from 1 to 3 depending on theproperties of the feed. For liquid or semiliquid feed a steam to feedratio may be at least 0.001, at least 0.01, at least 0.02, or atleast 1. For solid and/or semisolid feed a steam to feed ratio may be atleast 1, at least 2, at least 3, at least 5 or at least 10. Varying theamount of steam also changes the ratio of carbon monoxide to carbondioxide. The ratio of carbon monoxide to carbon dioxide in the producedgas may be varied from 0.01 to 10, or from 0.02 to 6, or from 0.03 to 5,or from 1 to 4 by altering the weight ratio of steam to feed in thecontacting zone. For example, by increasing the ratio of steam to feedin the contacting zone the ratio of carbon monoxide to carbon dioxide isdecreased.

The ratio of hydrogen source to feed may also be altered to alter theproperties of the crude product. For example, increasing the ratio ofthe hydrogen source to feed may result in crude product that has anincreased VGO content per gram of crude product.

In some embodiments, the feed may include significant amounts of sulfuras described herein which may be converted to hydrogen sulfide duringcontacting of the feed using systems, method and/or catalysts describedherein. The feed may also include entrained hydrogen sulfide gas priorto contacting. Sulfur, present as organosulfur or hydrogen sulfide isknown to poison and/or reduce the activity of catalysts used inprocessing of feeds to make commercial products. In some refineryoperations, feeds are treated to remove sulfur prior to treatment toobtain commercial products such as transportation fuel, thus a sulfurresistant catalyst are desirable. A content of sulfur, measured ashydrogen sulfide, per gram of feed, ranging from about 0.00001 grams toabout 0.01 grams or from about 0.0001 grams to about 0.001 gramshydrogen sulfide may poison and/or reduce the activity of conventionalcatalysts used for hydrotreating and/or catalytic cracking processes.

In some embodiments, contact of the feed with a hydrogen source in thepresence of the inorganic salt catalyst and a sulfur-containing compoundmay produce a total product that includes a crude product and/or gas.The feed, in some embodiments, is contacted in the presence of hydrogensulfide for at least 500 hours, at least 1000 hours, or at least 2000hours without replacement of the inorganic salt catalyst. The presenceof sulfur, in some embodiments, may enhance the production of carbonoxide gases (for example, carbon monoxide and carbon dioxide) when afeed is contacted with a hydrogen source and steam in the presence ofsulfur containing compounds relative to contacting under the sameconditions in the absence of sulfur. In some embodiments, contact of thefeed with a hydrogen source in the presence of the inorganic saltcatalyst and hydrogen sulfide produces a total product that has a carbonoxide gases content, per gram of feed, of at least 0.2 grams, at least0.5 grams, at least 0.8 grams, or at least 0.9 grams of carbon oxidegases.

In certain embodiments, contact of the feed with the inorganic saltcatalyst in the presence of light hydrocarbons and/or steam yields moreliquid hydrocarbons and less coke in a crude product than contact of afeed with an inorganic salt catalyst in the presence of hydrogen andsteam. In embodiments that include contact of the feed with methane inthe presence of the inorganic salt catalyst, at least a portion of thecomponents of the crude product may include atomic carbon and hydrogen(from the methane), which has been incorporated into the molecularstructures of the components.

In certain embodiments, the volume of crude product produced from a feedcontacted with the hydrogen source in the presence of the inorganic saltcatalyst is at least 5% greater, at least 10% greater, or at least 15%,or at most 100% greater than a volume of crude product produced from athermal process at STP. The total volume of crude product produced bycontact of the feed with the inorganic salt catalyst may be at least 110vol % of the volume of the feed at STP. The increase in volume isbelieved to be due to a decrease in density. Lower density may generallybe at least partially caused by hydrogenation of the feed.

In certain embodiments, a feed having, per gram of feed, at least 0.02grams, at least 0.05 grams, or at least 0.1 grams of sulfur, and/or atleast 0.001 grams of Ni/V/Fe is contacted with a hydrogen source in thepresence of an inorganic salt catalyst without diminishing the activityof the catalyst.

In some embodiments, the inorganic salt catalyst can be regenerated, atleast partially, by removal of one or more components that contaminatethe catalyst. Contaminants include, but are not limited to, metals,sulfides, nitrogen, coke, or mixtures thereof. Sulfide contaminants maybe removed from the used inorganic salt catalyst by contacting steam andcarbon dioxide with the used catalyst to produce hydrogen sulfide.Nitrogen contaminants may be removed by contacting the used inorganicsalt catalyst with steam to produce ammonia. Coke contaminants may beremoved from the used inorganic salt catalyst by contacting the usedinorganic salt catalyst with steam and/or methane to produce hydrogenand carbon oxides. In some embodiments, one or more gases are generatedfrom a mixture of used inorganic salt catalyst and residual feed.

In certain embodiments, a mixture of used inorganic salt catalyst (forexample, a supported inorganic salt catalyst, a mixture of ZrO₂ and CaO,a mixture of ZrO₂ and MgO, K₂CO₃/Rb₂CO₃/Cs₂CO₃; KOH/Al₂O₃; Cs₂CO₃/CaCO₃;or NaOH/KOH/LiOH/ZrO₂), unreacted feed and/or residue and/or coke may beheated to a temperature in a range from about 700-1000° C. or from about800-900° C. until the production of gas and/or liquids is minimal in thepresence of steam, hydrogen, carbon dioxide, and/or light hydrocarbonsto produce a liquid phase and/or gas. The gas may include an increasedquantity of hydrogen and/or carbon dioxide relative to reactive gas. Forexample, the gas may include from about 0.1-99 moles or from about 0.2-8moles of hydrogen and/or carbon dioxide per mole of reactive gas. Thegas may contain a relatively low amount of light hydrocarbons and/orcarbon monoxide. For example, less than about 0.05 grams of lighthydrocarbons per gram of gas and less than about 0.01 grams of carbonmonoxide per gram of gas. The liquid phase may contain water, forexample, greater than 0.5-0.99 grams, or greater than 0.9-0.9 grams ofwater per gram of liquid.

In some embodiments, the used catalyst and/or solids in the contactingzone may be treated to recover metals (for example, vanadium and/ornickel) from the used catalyst and/or solids. The used catalyst and/orsolids may be treated using generally known metal separation techniques,for example, heating, chemical treating, and/or gasification.

EXAMPLES

Non-limiting examples of catalyst preparations, testing of catalysts,and systems with controlled contacting conditions are set forth below.

Example 1 TAP Testing of a K₂CO₃₁Rb₂CO₃/Cs₂CO₃ Catalyst and theIndividual Inorganic Salts

In all TAP testing, a 300 mg sample was heated in a reactor of a TAPsystem from room temperature (about 27° C.) to 500° C. at a rate ofabout 50° C. per minute. Emitted water vapor and carbon dioxide gas weremonitored using a mass spectrometer of the TAP system.

The K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst supported on alumina showed a currentinflection of greater than 0.2 volts for emitted carbon dioxide and acurrent inflection of 0.01 volts for emitted water from the inorganicsalt catalyst at about 360° C. The minimum TAP temperature was about360° C., as determined by plotting the log 10 of the ion current versustemperature. FIG. 10 is a graphical representation of log 10 plots ofion current of emitted gases from the K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst (“log(I)”) versus temperature (“T”). Curves 232 and 234 are log 10 values forthe ion currents for emitted water and CO₂ from the inorganic saltcatalyst. Sharp inflections for emitted water and CO₂ from the inorganicsalt catalyst occurs at about 360° C.

In contrast to the K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst, potassium carbonate andcesium carbonate had non-detectable current inflections at 360° C. forboth emitted water and carbon dioxide.

The substantial increase in emitted gas for the K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst demonstrates that inorganic salt catalysts composed of two ormore different inorganic salts may be more disordered than theindividual pure carbonate salts.

Example 2 DSC Testing of an Inorganic Salt Catalyst and IndividualInorganic Salts

In all DSC testing, a 10 mg sample was heated to 520° C. at a rate of10° C. per min, cooled from 520° C. to 0.0° C. at rate of 10° C. perminute, and then heated from 0° C. to 600° C. at a rate of 10.0° C. permin using a differential scanning calorimeter (DSC) Model DSC-7,manufactured by Perkin-Elmer (Norwalk, Conn., U.S.A.).

DSC analysis of a K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst during second heating ofthe sample shows that the salt mixture exhibited a broad heat transitionbetween 219° C. and 260° C. The midpoint of the temperature range wasabout 250° C. The area under heat transition curve was calculated to be−1.75 Joules per gram. The beginning of crystal disorder was determinedto start at the minimum DSC temperature of 219° C.

In contrast to these results, no definite heat transitions were observedfor cesium carbonate.

DSC analysis of a mixture of Li₂CO₃, Na₂CO₃, and K₂CO₃ during the secondheating cycle shows that the Li₂CO₃/Na₂CO₃/K₂CO₃ mixture exhibited asharp heat transition between 390° C. to 400° C. The midpoint of thetemperature range was about 385° C. The area under heat transition curvewas calculated to be −182 Joules per gram. The beginning of mobility isdetermined to start at the minimum DSC temperature of 390° C. The sharpheat transition indicates a substantially homogeneous mixture of salts.

Example 3 Ionic Conductivity Testing of an Inorganic Salt Catalysts oran Individual Inorganic Salt Relative to K₂CO₃

All testing was conducted by placing 3.81 cm (1.5 inches) of theinorganic salt catalysts or the individual inorganic salts in a quartzvessel with platinum or copper wires separated from each other, butimmersed in the sample in a muffle furnace. The wires were connected toa 9.55 volt dry cell and a 220,000 ohm current limiting resistor. Themuffle furnace was heated to 600° C. and the current was measured usinga microammeter.

FIG. 11 is a graphical representation of log plots of the sampleresistance relative to potassium carbonate resistance (“log (rK₂CO₃)”)versus temperature (“T”). Curves 240, 242, 244, 246, and 248 are logplots of K₂CO₃ resistance, CaO resistance, K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalystresistance, Li₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst resistance, andNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst resistance, respectively.

CaO (curve 242) exhibits relatively large stable resistance relative toK₂CO₃ (curve 240) at temperatures in a range between 380-500° C. Astable resistance indicates an ordered structure and/or ions that tendnot to move apart from one another during heating. TheK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst, Li₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst, andNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst (see curves 244, 246, and 248) showa sharp decrease in resistivity relative to K₂CO₃ at temperatures in arange from 350-500° C. A decrease in resistivity generally indicatesthat current flow was detected during application of voltage to thewires embedded in the inorganic salt catalyst. The data from FIG. 11demonstrate that the inorganic salt catalysts are generally more mobilethan the pure inorganic salts at temperatures in a range from 350-600°C.

FIG. 12 is a graphical representation of log plots ofNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst resistance relative to K₂CO₃resistance (“log (rK₂CO₃)”) versus temperature (“T”). Curve 250 is aplot of a ratio of Na₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst resistancerelative to K₂CO₃ resistance (curve 240) versus temperature duringheating of the Na₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst. After heating, theNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst was cooled to room temperature andthen heated in the conductivity apparatus. Curve 252 is a log plot ofNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst resistance relative to K₂CO₃resistance versus temperature during heating of the inorganic saltcatalyst after being cooled from 600° C. to 25° C. The ionicconductivity of the reheated Na₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalystincreased relative to the ionic conductivity of the originalNa₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst.

From the difference in ionic conductivities of the inorganic saltcatalyst during the first heating and second heating, it may be inferredthat the inorganic salt catalyst forms a different form (a second form)upon cooling that is not the same as the form (a first form) before anyheating.

Example 4 Flow Property Testing of an Inorganic Salt Catalyst

A 1-2 cm thick layer of powdered K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst was placedin a quartz dish. The dish was placed in a furnace and heated to 500° C.for about 1 hour. To determine flow properties of the catalyst, the dishwas manually tilted in the oven after heating. The K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst did not flow. When pressed with a spatula, the catalyst had aconsistency of taffy.

In contrast, the individual carbonate salts were free flowing powdersunder the same conditions.

A Na₂CO₃/K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst became liquid and readily flowed(similar, for example, to water) in the dish under the same conditions.

Examples 5 and 6 Contact of a Feed with a Hydrogen Source in thePresence of a K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst and Steam

The following equipment and general procedure was used in Examples 5-23except where variations are described.

Reactor: A 250 mL Hastelloy C Parr Autoclave (Parr Model #4576) rated at35 MPa working pressure (5000 psi) at 500° C., was fitted with amechanical stirrer and an 800 watt Gaumer band heater on a Eurothermcontroller capable of maintaining the autoclave at ±5° C. from ambientto 625° C., a gas inlet port, a steam inlet port, one outlet port, and athermocouple to register internal temperature. Prior to heating, the topof the autoclave was insulated with glass cloth.

Addition Vessel: An addition vessel (a 250 mL, 316 stainless steel hokevessel) was equipped with a controlled heating system, suitable gascontrol valving, a pressure relief device, thermocouples, a pressuregauge, and a high temperature control valve (Swagelok Valve # SS-4UW)capable of regulating flow of a hot, viscous, and/or pressurized feed ata flow rate from 0-500 g/min. An outlet side of the high temperaturecontrol valve was attached to the first inlet port of the reactor afterfeed was charged to the addition vessel. Prior to use, the additionvessel line was insulated.

Product Collection: Vapor from the reactor exited the outlet port of thereactor and was introduced into a series of cold traps of decreasingtemperatures (dip tubes connected to a series of 150 mL, 316 stainlesssteel hoke vessels). Liquid from the vapor was condensed in the coldtraps to form a gas stream and a liquid condensate stream. Flow rate ofthe vapor from the reactor and through the cold traps was regulated, asneeded, using a back pressure regulator. A rate of flow and a total gasvolume for the gas stream exiting the cold traps were measured using awet test meter (Ritter Model # TG 05 Wet Test Meter). After exiting thewet test meter, the gas stream was collected in a gas bag (a Tedlar gascollection bag) for analysis. The gas was analyzed using GC/MS(Hewlett-Packard Model 5890, now Agilent Model 5890; manufactured byAgilent Technologies, Zion Ill., U.S.A.). The liquid condensate streamwas removed from the cold traps and weighed. Crude product and waterwere separated from the liquid condensate stream. The crude product wasweighed and analyzed.

Procedure: Cerro Negro (137.5 grams) was charged to the addition vessel.The feed had an API gravity of 6.7. The feed had, per gram of feed, asulfur content of 0.042 grams, a nitrogen content of 0.011 grams, and atotal Ni/V content of 0.009 grams. The feed was heated to 150° C. TheK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst (31.39 grams) was charged to the reactor.

The K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst was prepared by combining of 16.44grams of K₂CO₃, 19.44 grams of Rb₂CO₃, and 24.49 grams of Cs₂CO₃. TheK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst had a minimum TAP temperature of 360° C.The K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst had a DSC temperature of 250° C. Theindividual salts (K₂CO₃, Rb₂CO₃, and Cs₂CO₃) did not exhibit DSCtemperatures in a range from 50-500° C. This TAP temperature is abovethe DSC temperature of the inorganic salt catalyst and below the DSCtemperature of the individual metal carbonates.

The catalyst was heated rapidly to 450° C. under an atmospheric pressureflow of methane of 250 cm³/min. After reaching the desired reactiontemperature, steam at a rate of 0.4 mL/min, and methane at rate of 250cm³/min, was metered to the reactor. The steam and methane werecontinuously metered during the addition of the feed to the reactor overabout 2.6 hours. The feed was pressurized into the reactor using 1.5 MPa(229 psi) of CH₄ over 16 minutes. Residual feed (0.56 grams) remained inthe addition vessel after the addition of the feed was complete. Adecrease in temperature to 370° C. was observed during the addition ofthe feed.

The catalyst/feed mixture was heated to a reaction temperature of 450°C. and maintained at that temperature for about 2 hours. After twohours, the reactor was cooled and the resulting residue/catalyst mixturewas weighed to determine a percentage of coke produced and/or notconsumed in the reaction.

From a difference in initial catalyst weight and coke/catalyst mixtureweight, 0.046 grams of coke remained in the reactor per gram of feed.The total product included 0.87 grams of a crude product with an averageAPI gravity of 13 and gas. The gas included unreacted CH₄, hydrogen, C₂and C₄-C₆ hydrocarbons, and CO₂ (0.08 grams of CO₂ per gram of gas).

The crude product had, per gram of crude product, 0.01 grams of sulfurand 0.000005 grams of a total Ni and V. The crude product was notfurther analyzed.

In Example 6, the reaction procedures, conditions, feed, and catalystwere the same as in Example 5. The crude product of Example 6 wasanalyzed to determine boiling range distributions for the crude product.The crude product had, per gram of crude product, 0.14 grams of naphtha,0.19 grams of distillate, 0.45 grams of VGO, and residue content of0.001 grams, and non-detectable amounts of coke.

Examples 5 and 6 demonstrate that contact of the feed with a hydrogensource in the presence of at most 3 grams of catalyst per 100 grams offeed produces a total product that includes a crude product that is aliquid mixture at STP. The crude product had a residue content of atmost 30% of the residue content of the feed. The crude product had asulfur content and total Ni/V content of at most 90% of the sulfurcontent and Ni/V content of the feed.

The crude product included at least 0.001 grams of hydrocarbons with aboiling range distribution of at most 200° C. at 0.101 MPa, at least0.001 grams of hydrocarbons with a boiling range distribution between200-300° C. at 0.101 MPa, at least 0.001 grams of hydrocarbons with aboiling range distribution between 400-538° C. (1000° F.) at 0.101 MPa.

Examples 7-8 Contact of a Feed with a Hydrogen Source in the Presence ofthe K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst and Steam

The reaction procedures, conditions, and the K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst in Examples 7 and 8 were the same as in Example 5, except that130 grams of feed (Cerro Negro) and 60 grams of the K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst were used. In Example 7, methane was used as the hydrogensource. In Example 8, hydrogen gas was used as the hydrogen source. Agraphical representation of the amounts of non-condensable gas, crudeproduct, and coke is depicted in FIG. 13. Bars 254 and 256 represent wt% coke produced, bars 258 and 260 represent wt % liquid hydrocarbonsproduced, and bars 262 and 264 represent wt % gas produced, based on theweight of the feed.

In Example 7, 93 wt % of crude product (bar 260), 3 wt % of gas (bar264), and 4 wt % of coke (bar 256), based on the weight of the CerroNegro, was produced.

In Example 8, 84 wt % of crude product (bar 258), 7 wt % of gas (bar262), and 9 wt % of coke were produced (bar 254), based on the weight ofthe Cerro Negro.

Examples 7 and 8 provide a comparison of the use of methane as ahydrogen source to the use of hydrogen gas as a hydrogen source. Methaneis generally less expensive to produce and/or transport than hydrogen,thus a process that utilizes methane is desirable. As demonstrated,methane is at least as effective as hydrogen gas as a hydrogen sourcewhen contacting a feed in the presence of an inorganic salt catalyst toproduce a total product.

Examples 9-10 Producing a Crude Product with Selected API Gravity

The apparatus, reaction procedure and the inorganic salt catalyst werethe same as in Example 5, except that the reactor pressure was varied.

Example 9, the reactor pressure was 0.1 MPa (14.7 psi) during thecontacting period. A crude product with API gravity of 25 at 15.5° C.was produced. The total product had hydrocarbons with a distribution ofcarbon numbers in a range from 5 to 32 (see curve 266 in FIG. 14).

In Example 10, the reactor pressure was 3.4 MPa (514.7 psi) during thecontacting period. A crude product with API gravity of 51.6 at 15.5° C.was produced. The total product had hydrocarbons with a distribution ofcarbon numbers in a range from 5 to 15 (see curve 268 in FIG. 12).

These examples demonstrate methods for contacting the feed with hydrogenin the presence of an inorganic salt catalyst at various pressures toproduce a crude product with a selected API gravity. By varying thepressure, a crude product with a higher or lower API gravity wasproduced.

Examples 11-12 Contact of a Feed in the Presence of aK₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst or Silicon Carbide in the Absence of anExternal Hydrogen Source

In Examples 11 and 12, the apparatus, feed, and reaction procedure werethe same as in Example 5, except that the feed and catalyst (or siliconcarbide) were directly charged into the reactor at the same time. Carbondioxide (CO₂) was used as a carrier gas. In Example 11, 138 grams ofCerro Negro was combined with 60.4 grams of the K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst (same catalyst as in Example 5). In Example 12, 132 g of CerroNegro was combined with 83.13 grams of silicon carbide (40 mesh,Stanford Materials; Aliso Viejo, Calif.). Such silicon carbide isbelieved to have low, if any, catalytic properties under the processconditions described herein.

In each example, the mixture was heated to a reaction temperature of500° C. over a period of about 2 hours. The CO₂ was metered into thereactor at a rate of 100 cm³/min. Vapor generated from the reactor wascollected in the cold traps and a gas bag using a back pressure of about3.2 MPa (479.7 psi). Crude product from the cold traps was consolidatedand analyzed.

In Example 11, 36.82 grams (26.68 wt %, based on the weight of the feed)of a colorless hydrocarbon liquid with API gravity of at least 50 wasproduced from contact of the feed with the inorganic salt catalyst inthe carbon dioxide atmosphere.

In Example 12, 15.78 grams (11.95 wt %, based on the weight of the feed)of a yellow hydrocarbon liquid with an API gravity of 12 was producedfrom contact of the feed with silicon carbide in the carbon dioxideatmosphere.

Although the yield in Example 11 is low, the in-situ generation of ahydrogen source in the presence of the inorganic salt catalyst isgreater than the in-situ generation of hydrogen under non-catalyticconditions. The yield of crude product in Example 12 is one-half of theyield of crude product in Example 11. Example 11 also demonstrates thathydrogen is generated during contact of the feed in the presence of theinorganic salt and in the absence of a gaseous hydrogen source.

Examples 13-16 Contact of a Feed with a Hydrogen Source in the Presenceof K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst, Calcium Carbonate, and Silicon Carbideat Atmospheric Conditions

The apparatus, reaction procedure, feed and the inorganic salt catalystwere the same as in Example 5, except that the Cerro Negro was addeddirectly to the reactor instead of addition through the addition vesseland hydrogen gas was used as the hydrogen source. The reactor pressurewas 0.101 MPa (14.7 psi) during the contacting period. The hydrogen gasflow rate was 250 cm³/min. Reaction temperatures, steam flow rates, andpercentages of crude product, gas, and coke produced are tabulated inTable 1 in FIG. 15.

In Examples 13 and 14, the K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst was used. InExample 13, the contacting temperature was 375° C. In Example 14, thecontacting temperature was in a temperature range from 500-600° C.

As shown in Table 1 (FIG. 15), for Examples 13 and 14, when thetemperature was increased from 375° C. to 500° C., production of gasincreased from 0.02 grams to 0.05 grams of gas per gram of totalproduct. Coke production, however, decreased from 0.17 grams to 0.09grams of coke per gram of feed at the higher temperature. The sulfurcontent of the crude product also decreased from 0.01 grams to 0.008grams of sulfur per gram of crude product at the higher temperature.Both crude products had atomic H/C of 1.8.

In Example 15, a feed was contacted with CaCO₃ under conditions similarto the conditions described for Example 14. Percentages of crudeproduct, gas, and coke production are tabulated in Table 1 in FIG. 13.Gas production increased in Example 15 relative to the gas production inExample 14. Desulfurization of the feed was not as effective as inExample 14. The crude product produced in Example 15 had, per gram ofcrude product, 0.01 grams of sulfur as compared to the sulfur content of0.008 grams per gram of crude product for the crude product produced inExample 14.

Example 16 is a comparative example for Example 14. In Example 16, 83.13grams of silicon carbide instead of the inorganic salt catalyst wascharged to the reactor. Gas production and coke production significantlyincreased in Example 16 relative to the gas production and cokeproduction in Example 14. Under these non-catalytic conditions, 0.22grams of coke per gram of crude product, 0.25 grams of non-condensablegas, and 0.5 grams of crude product were produced. The crude productproduced in Example 16 had 0.036 grams of sulfur per gram of crudeproduct, compared to of 0.01 grams of sulfur per gram of crude productproduced in Example 14.

These examples demonstrated that the catalysts used in Examples 13 and14 provide improved results over non-catalytic conditions andconventional metal salts. At 500° C., and a hydrogen flow rate of 250cm³/min, the amounts of coke and non-condensable gas were significantlylower than the amounts of coke and of non-condensable gas produced undernon-catalytic conditions.

In examples using inorganic salt catalysts (See Examples 13-14 in Table1, FIG. 15), a decrease was observed in the weight percent of producedgas relative to the produced gas formed during the control experiment(for example, Example 16 in Table 1, FIG. 15). From the quantity ofhydrocarbons in the produced gas, the thermal cracking of the feed isestimated to be at most 20 wt %, at most 15 wt %, at most 10 wt %, atmost 5 wt %, or none, based on the total amount of feed contacted with ahydrogen source.

Examples 17 and 18 Contact of a Feed with a Gaseous Hydrogen Source Inthe Presence of Water and a K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst or SiliconCarbide

Apparatus in Examples 17 and 18 were the same as in Example 5 exceptthat hydrogen gas was used as the hydrogen source. In Example 17, 130.4grams of Cerro Negro was combined with 30.88 grams of theK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst to form a feed mixture. In Example 18,139.6 grams of Cerro Negro was combined with 80.14 grams of siliconcarbide to form the feed mixture.

The feed mixture was charged directly into the reactor. The hydrogen gaswas metered at 250 cm³/min into the reactor during the heating andholding periods. The feed mixture was heated to 300° C. over about 1.5hours and maintained at 300° C. for about 1 hour. The reactiontemperature was increased to 400° C. over about 1 hour and maintained at400° C. for about 1 hour. After the reaction temperature reached 400°C., water was introduced into the reactor at a rate of 0.4 g/min incombination with the hydrogen gas. Water and hydrogen were metered intothe reactor for the remaining heating and holding periods. Aftermaintaining the reaction mixture at 400° C., the reaction temperaturewas increased to 500° C. and maintained at 500° C. for about 2 hours.Generated vapor from the reactor was collected in the cold traps and agas bag. Liquid product from the cold traps was consolidated andanalyzed.

In Example 17, 86.17 grams (66.1 wt %, based on the weight of the feed)of a dark reddish brown hydrocarbon liquid (crude product) and water(97.5 g) were produced as a vapor from contact of the feed with theK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst in the hydrogen atmosphere.

In Example 18, water vapor and a small amount of gas was produced fromthe reactor. The reactor was inspected, and a dark brown viscoushydrocarbon liquid was removed from the reactor. Less than 50 wt % ofthe dark brown viscous liquid was produced from contact of the feed withsilicon carbide in the hydrogen atmosphere. A 25% increase in yield ofcrude product was observed in Example 17 relative to a yield of crudeproduct produced in Example 18.

Example 17 demonstrates an improvement of the properties of the crudeproduct produced using methods described herein relative to a crudeproduct produced using hot water. Specifically, the crude product inExample 17 was lower boiling than the crude product from Example 18, asdemonstrated by the crude product produced in Example 18 not being ableto be produced as a vapor. The crude product produced in Example 17 hadenhanced flow properties relative to the crude product produced inExample 18, as determined by visual inspection.

Examples 19-20 Contact of a Feed with a Hydrogen Source in the Presenceof a K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst to Produce a Crude Product withIncreased Volume Relative to a Crude Product Volume Produced underNon-Catalytic Conditions

The apparatus, feed, inorganic catalyst, and reaction procedure was thesame as described in Example 5, except the feed was directly charged tothe reactor and hydrogen gas was used as the hydrogen source. The feed(Cerro Negro) had an API gravity 6.7 and a density of 1.02 g/mL at 15.5°C.

In Example 19, 102 grams of the feed (about 100 mL of feed) and 31 gramsof K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst were charged to the reactor. A crudeproduct (87.6 grams) with an API gravity of 50 and a density of 0.7796g/mL at 15.5° C. (112 mL) was produced.

In Example 20, 102 grams of feed (about 100 mL of feed) and 80 grams ofsilicon carbide were charged to the reactor. A crude product (70 grams)of with an API gravity of 12 and a density of 0.9861 g/mL at 15.5° C.(about 70 mL) was produced.

Under these conditions, the volume of the crude product produced fromExample 19 was approximately 10% greater than the volume of the feed.The volume of the crude product produced in Example 20 was significantlyless (40% less) than the volume of crude product produced in Example 19.A significant increase in volume of product enhances a producer'sability to generate more volume of crude product per volume of inputcrude.

Example 21 Contact of a Feed with a Hydrogen Source in the Presence of aK₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst, Sulfur, and Coke

The apparatus and reaction procedure were the same as in Example 5,except that the steam was metered into the reactor at 300 cm³/min. TheK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst was prepared by combining 27.2 grams ofK₂CO₃, 32.2 grams of Rb₂CO₃ and 40.6 grams of Cs₂CO₃.

The feed (130.35 grams) and K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst (31.6 grams)was charged to the reactor. The Cerro Negro crude included, per gram offeed, 0.04 grams total aromatics content in a boiling range distributionbetween 149-260° C. (300-500° F.), 0.000640 grams of nickel and vanadiumcombined, 0.042 grams of sulfur, and 0.56 grams of residue. API gravityof the feed was 6.7.

Contact of the feed with methane in the presence of theK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst produced, per gram of feed, 0.95 grams oftotal product, and 0.041 grams of coke.

The total product included, per gram of total product, 0.91 grams ofcrude product and 0.028 grams of hydrocarbon gas. The total gascollected included, per mole of gas, 0.16 moles of hydrogen, 0.045 molesof carbon dioxide, and 0.025 moles of C₂ and C₄-C₆ hydrocarbons, asdetermined by GC/MS. The balance of the gas was methane, air, carbonmonoxide, and a trace (0.004 moles) of evaporated crude product.

The crude product was analyzed using a combination of gas chromatographyand mass spectrometry. The crude product included a mixture ofhydrocarbons with a boiling range between 100-538° C. The total liquidproduct mixture included 0.006 grams ethyl benzene (a monocyclic ringcompound with a boiling point of 136.2° C. at 0.101 MPa) per gram ofmixture. This product was not detected in the feed.

The used catalyst (“first used catalyst”) was removed from the reactor,weighed, and then analyzed. The first used catalyst had an increase inweight from 31.6 grams to a total weight of 37.38 grams (an increase of18 wt %, based on the weight of the original K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst). The first used catalyst included 0.15 grams of additionalcoke, 0.0035 grams of sulfur, 0.0014 grams of Ni/V, and 0.845 grams ofK₂CO₃/Rb₂CO₃/Cs₂CO₃ per gram of used catalyst.

Additional feed (152.71 grams) was contacted with the first usedcatalyst (36.63 grams) to produce 150 grams of recovered total productafter losses. The total product included, per gram of total product,0.92 grams of liquid crude product, 0.058 grams of additional coke, and0.017 grams of gas. The gas included, per mole of gas, 0.18 moles ofhydrogen, 0.07 grams of carbon dioxide, and 0.035 moles of C₂-C₆hydrocarbons. The balance of the gas was methane, nitrogen, some air,and traces of evaporated oil product (<1% mole).

The crude product included a mixture of hydrocarbons with a boilingrange between 100-538° C. The portion of the mixture with a boilingrange distribution below 149° C. included, per mole of total liquidhydrocarbons, 0.018 mole % of ethyl benzene, 0.04 mole % of toluene,0.03 mole % of meta-xylene, and 0.060 mole % of para-xylene (monocyclicring compounds with a boiling points below 149° C. at 0.101 MPa). Theseproducts were not detectable in the feed.

The used catalyst (“second used catalyst”) was removed from the reactor,weighed, and then analyzed. The second used catalyst had an increase inweight from 36.63 grams to a total weight of 45.44 grams (an increase of43 wt %, based on the weight of the original K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst). The second used catalyst included 0.32 grams of coke, and0.01 grams of sulfur, and 0.67 grams per gram of second used catalyst.

Additional feed (104 grams) was contacted with the second used catalyst(44.84 grams) to produce, per gram of feed, 104 grams of total productand 0.114 grams of coke was collected. A portion of the coke wasattributed to coke formation in the addition vessel due to overheatingthe addition vessel since 104.1 grams of the 133 grams of feedtransferred was feed.

The total product included, per gram of total product, 0.86 grams ofcrude product and 0.025 grams of hydrocarbon gas. The total gasincluded, per mole of gas, 0.18 moles of hydrogen, 0.052 moles of carbondioxide, and 0.03 moles of C₂-C₆ hydrocarbons. The balance of the gaswas methane, air, carbon monoxide, hydrogen sulfide, and a small traceof evaporated oil.

The crude product included a mixture of hydrocarbons with a boilingrange between 100-538° C. The portion of the mixture with a boilingrange distribution below 149° C. included, per gram of hydrocarbonmixture, 0.021 grams ethyl benzene, 0.027 grams of toluene, 0.042 gramsof meta-xylene, and 0.020 grams of para-xylene, determined as before byGC/MS.

The used catalyst (“third used catalyst”) was removed from the reactor,weighed, and then analyzed. The third used catalyst had an increase inweight from 44.84 grams to a total weight of 56.59 grams (an increase of79 wt %, based on the weight of the original K₂CO₃/Rb₂CO₃/Cs₂CO₃catalyst). Detailed elemental analysis of the third used catalyst wasperformed. The third used catalyst included, per gram of additionalmatter, 0.90 grams of carbon, 0.028 grams of hydrogen, 0.0025 grams ofoxygen, 0.046 grams of sulfur, 0.017 grams of nitrogen, 0.0018 grams ofvanadium, 0.0007 grams of nickel, 0.0015 grams of iron, and 0.00025grams of chloride with the balance being other transition metals such aschromium, titanium, and zirconium.

As demonstrated in this example, coke, sulfur, and/or metals depositedon and/or in the inorganic salt catalyst do not affect the overall yieldof crude product (at least 80% for each run) produced by contact of afeed with a hydrogen source in the presence of the inorganic saltcatalyst. The crude product had a monocyclic aromatics content at least100 times the monocyclic ring aromatics content of the feed in a boilingrange distribution below 149° C.

For the three runs, the average crude product yield (based on the weightof the feed) was 89.7 wt %, with a standard deviation of 2.6%; theaverage coke yield was 7.5 wt % (based on the weight of the feed), witha standard deviation of 2.7%, and the average weight yield of gaseouscracked hydrocarbons was 2.3 wt % (based on the weight of the feed) witha standard deviation of 0.46%. The comparatively large standarddeviation of both liquid and coke was due to the third trial, in whichthe temperature controller of the feed vessel failed, overheating thefeed in the addition vessel. Even so, there is no apparent significantdeleterious effect of even the large amounts of coke tested here on theactivity of the catalyst system.

The ratio of C₂ olefins to total C₂ was 0.19. The ratio of C₃ olefin tototal C₃ was 0.4. The alpha olefins to internal olefins ratio of the C₄hydrocarbons was 0.61. The C₄ cis/trans olefins ratio was 6.34. Thisratio was substantially higher than the predicted thermodynamic C₄cis/trans olefins ratio of 0.68. The alpha olefins to internal olefinsratio of the C₅ hydrocarbons was 0.92. This ratio was greater than thepredicted thermodynamic C₅ alpha olefins to C₅ internal olefins ratio of0.194. The C₅ cis/trans olefins ratio was 1.25. This ratio was greaterthan the predicted thermodynamic C₅ cis/trans olefins ratio of 0.9.

Example 22 Contact of a Relatively High Sulfur Containing Feed with aHydrogen Source in the Presence of the K₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst

The apparatus and reaction procedure were the same as described inExample 5, except that the feed, methane, and steam were continuouslyfed to the reactor. The level of feed in the reactor was monitored usinga change in weight of the reactor. Methane gas was continuously meteredat 500 cm³/min to the reactor. Steam was continuously metered at 6 g/minto the reactor.

The inorganic salt catalyst was prepared by combining 27.2 grams ofK₂CO₃, 32.2 grams of Rb₂CO₃ and 40.6 grams of Cs₂CO₃. TheK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst (59.88 grams) was charged to the reactor.

A feed (bitumen, Lloydminster, Canada) having an API gravity of 9.4, asulfur content of 0.02 grams of sulfur, and a residue content of 0.40grams, per gram of feed, was heated in the addition vessel to 150° C.The hot bitumen was continuously metered from the addition vessel at10.5 g/min to the reactor in an attempt to maintain the feed liquidlevel of 50% of the reactor volume, however, the rate was insufficientto maintain that level.

The methane/steam/feed was contacted with the catalyst at an averageinternal reactor temperature of 456° C. Contacting of themethane/steam/feed with the catalyst produced a total product (in thisexample in the form of the reactor effluent vapor).

A total of 1640 grams of feed was processed over 6 hours. From adifference in initial catalyst weight and residue/catalyst mixtureweight, 0.085 grams of coke per gram of feed remained in the reactor.From contact of the feed with the methane in the presence of theK₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst, 0.93 grams of total product per gram offeed was produced. The total product included, per gram of totalproduct, 0.03 grams of gas and 0.97 grams of crude product, excludingthe amount of methane and water used in the reaction.

The gas included, per gram of gas, 0.014 grams of hydrogen, 0.018 gramsof carbon monoxide, 0.08 grams of carbon dioxide, 0.13 grams of hydrogensulfide, and 0.68 grams of non-condensable hydrocarbons. From the amountof hydrogen sulfide generated, it may be estimated that the sulfurcontent of the feed was reduced by 18 wt %. As shown in this example,hydrogen, carbon monoxide, and carbon dioxide were produced. The molarratio of carbon monoxide to carbon dioxide was 0.4.

The C₂-C₅ hydrocarbons included, per gram of hydrocarbons, 0.30 grams ofC₂ compounds, 0.32 grams of C₃ compounds, 0.26 grams of C₄ compounds,and 0.10 grams of C₅ compounds. The weight ratio of iso-pentane ton-pentane in the non-condensable hydrocarbons was 0.3. The weight ratioof isobutane to n-butane in the non-condensable hydrocarbons was 0.189.The C₄ compounds had, per gram of C₄ compounds, a butadiene content of0.003 grams. A weight ratio of alpha C₄ olefins to internal C₄ olefinswas 0.75. A weight ratio of alpha C₅ olefins to internal C₅ olefins was1.08.

The data in Example 25 demonstrates that continuous processing of arelatively high sulfur feed with the same catalyst in the presence ofcoke did not diminish the activity of the inorganic salt catalyst, andproduced a crude product suitable for transportation.

Example 23 Contact of a Feed with a Hydrogen Source in the Presence of aK₂CO₃/Rb₂CO₃/Cs₂CO₃ Catalyst and Coke

The apparatus and reaction procedure was performed using conditions asdescribed in Example 22. The K₂CO₃/Rb₂CO₃/Cs₂CO₃ catalyst (56.5 grams)was charged to the reactor. A total of 2550 grams of feed was processedover 6 hours. From a difference in initial catalyst weight andresidue/catalyst mixture weight, 0.114 grams of coke per gram of feedremained in the reactor, based on the weight of the feed. A total of0.89 grams of total product per gram of feed was produced. The totalproduct included, per gram of total product, 0.04 grams of gas and 0.96grams of crude product, excluding the amount of methane and water usedin the reaction.

The gas included, per gram of gas, 0.021 grams of hydrogen, 0.018 gramsof carbon monoxide, 0.052 grams of carbon dioxide, 0.18 grams ofhydrogen sulfide, and 0.65 grams of non-condensable hydrocarbons. Fromthe amount of hydrogen sulfide produced, it may be estimated that thesulfur content of the feed was reduced by 14 wt %, based on the weightof the feed. As shown in this example, hydrogen, carbon monoxide, andcarbon dioxide were produced. The molar ratio of carbon monoxide tocarbon dioxide was 0.6.

The C₂-C₆ hydrocarbons included, per gram of C₂-C₆ hydrocarbons, 0.44grams of C₂ compounds, 0.31 grams of C₃ compounds, 0.19 grams of C₄compound and 0.068 grams of C₅ compounds. The weight ratio ofiso-pentane to n-pentane in the non-condensable hydrocarbons was 0.25.The weight ratio of iso-butane to n-butane in the non-condensablehydrocarbons was 0.15. The C₄ compounds had, per gram of C₄ compounds, abutadiene content of 0.003 grams.

This example demonstrates that repeated processing of the a relativelyhigh sulfur feed (2550 grams of feed) with the same catalyst (56.5grams) in the presence of coke did not diminish the activity of theinorganic salt catalyst, and produced a crude product suitable fortransportation.

Example 24 Contact of a Feed with a Hydrogen Source in the Presence ofCaO/ZrO₂ Catalyst to Produce a Total Product

The following reactor and conditions were used for Examples 24-27.

Reactor: A 250 mL Hastelloy C Parr Autoclave (Parr Model #4576) rated at35 MPa working pressure (5000 psi) at 500° C., was fitted with amechanical stirrer and an 800 watt Gaumer band heater on a Eurothermcontroller capable of maintaining the autoclave at ±5° C. from ambientto 625° C., a gas inlet port, a steam inlet port, one outlet port, and athermocouple to register internal temperature. Prior to heating, the topof the autoclave was insulated with glass cloth. The reactor includes ascreen with openings having a diameter of less than 16 mesh.

Addition Vessel: An addition vessel (a 250 mL, 316 stainless steel hokevessel) was equipped with a controlled heating system, suitable gascontrol valving, a pressure relief device, thermocouples, a pressuregauge, and a high temperature control valve (Swagelok Valve # SS-4UW)capable of regulating flow of a hot, viscous, and/or pressurized feed ata flow rate from 0-500 g/min. An outlet side of the high temperaturecontrol valve was attached to the first inlet port of the reactor afterfeed was charged to the addition vessel. Prior to use, the additionvessel line was insulated.

Product Collection: Vapor from the reactor exited the outlet port of thereactor and was introduced into a series of cold traps of decreasingtemperatures (dip tubes connected to a series of 150 mL, 316 stainlesssteel hoke vessels). Liquid from the vapor was condensed in the coldtraps to form a gas stream and a liquid condensate stream. Flow rate ofthe vapor from the reactor and through the cold traps was regulated, asneeded, using a back pressure regulator. A rate of flow and a total gasvolume for the gas stream exiting the cold traps were measured using awet test meter (Ritter Model # TG 05 Wet Test Meter). After exiting thewet test meter, the gas stream was collected in a gas bag (a Tedlar gascollection bag) for analysis. The gas was analyzed using GC/MS(Hewlett-Packard Model 5890, now Agilent Model 5890; manufactured byAgilent Technologies, Zion Ill., U.S.A.). The liquid condensate streamwas removed from the cold traps and weighed. Crude product and waterwere separated from the liquid condensate stream. The crude product wasweighed and analyzed.

Procedure: ZrO₂ (8.5 grams) was positioned on the screen in the reactor.The reactor was weighed to obtain an initial weight. Feed (asphaltenes,5.01 grams) was charged to the addition vessel. The feed was obtainedfrom deasphalting heavy oil. The feed had a density of 1.04 g/cc and asoftening point of 200° C. The feed had, per gram of feed, 0.0374 gramsof sulfur and 0.0124 grams of nitrogen.

The feed was heated to 150° C. A mixture of CaO (15.03 grams, 0.26moles) and ZrO₂ (20.05 grams, 0.16 moles) were added to the feed toproduce an inorganic salt catalyst/catalyst support/feed mixture. Theresulting mixture catalyst was metered to the reactor vessel over 20minutes (a calculated WHSV of 0.8 h⁻¹) to maintain the feed liquid levelof 50% of the reactor volume under a nitrogen atmosphere. Once aninternal temperature of the reactor reached 731° C., methane and water(26.06 grams charged as steam) were charged to the reaction vessel over1 hour. The reaction was run until little or no gas and/or liquidproduct was produced. The reactor was weighed at the end of the run toobtain a final reactor weight.

The total product included 1.06 grams of a crude product, and 8.152grams of gas. The gas included 0.445 grams of non-condensablehydrocarbons, 4.39 grams (0.10 moles) of CO₂, 3.758 grams (0.13 moles)of CO, 0.627 grams of H₂ gas, 0.03 grams of H₂S and 0.296 grams of coke.

The selectivity for products containing carbon was calculated based onthe weight of carbon containing products divided by weight of asphaltcharged to the reactor. For five experiments run as described in Example24 the mean selectivity for products containing carbon was determined tobe: 67 wt % for combined carbon monoxide and carbon dioxide, 7.47 wt %for non-condensable hydrocarbons and 19.88 wt % for crude product and4.94 wt % for coke.

This example demonstrates a method for contacting the feed with aninorganic salt catalyst/support mixture in the presence of a hydrogensource hydrogen source and steam to produce a crude product and gas andless than 0.1 grams of coke per gram of feed. In the presence of CaO,more the production of gas was increased relative to the production ofthan crude product. The molar ratio of CO to CO₂ was calculated to be1.3.

Example 25 Contact of a Feed with a Hydrogen Source in the Presence ofMgO/ZrO₂ Catalyst to Produce a Crude Product

The feed and apparatus was the same as described in Example 24. ZrO₂(8.59 grams) was placed on the screen in the reactor.

The feed was heated to 150° C. MgO catalyst (19.82 grams, 0.49 moles)and ZrO₂ (29.76 grams, 0.24 moles) were charged to the feed (9.92 grams)to produce an inorganic salt catalyst/catalyst support/feed mixture. Theresulting mixture catalyst was metered to the reactor vessel over 0.5hour (a calculated WHSV of 0.75 h⁻¹) to maintain the feed liquid levelof 50% of the reactor volume under a nitrogen atmosphere. Once aninternal temperature of the reactor reached 731° C., methane and water(48.1 grams charged as steam) were charged to the reaction vessel over0.5 hour. The reaction was run until little or no gas and/or liquidproduct was produced. The reactor was weighed at the end of the run toobtain a final reactor weight.

The total product included 1.92 grams of a crude product, and 18.45grams of gas. The gas included 1.183 grams of non-condensablehydrocarbons, 8.66 grams (0.19 moles) of CO₂, 7.406 grams (0.26 moles)of CO, 1.473 grams of H₂ gas, 0.125 grams of H₂S, and 0.0636 grams ofcoke. The molar ratio of CO to CO₂ was calculated to be 1.4.

The selectivity for products containing carbon was calculated based onthe weight of carbon containing products divided by weight of asphaltcharged to the reactor. For three experiments run as described inExample 25 the mean selectivity for products containing carbon wasdetermined to be: 65.88 wt % for combined carbon monoxide and carbondioxide, 11.74 wt % for non-condensable hydrocarbons and 12.35 wt % forcrude product and 8.78 wt % for coke.

This example demonstrates a method for contacting the feed with aninorganic salt catalyst/support mixture in the presence of a hydrogensource and steam to produce a crude product and gas and less than 0.1grams of coke per gram of feed. More gas than crude product was producedin the presence of MgO as compared to Example 24.

Example 26 Contact of a Feed with a Hydrogen Source in the Presence ofZrO₂ to Produce a Crude Product

The feed and apparatus was the same as described in Example 24. ZrO₂(8.56 grams) was placed on the screen in the reactor.

The feed was heated to 150° C. ZrO₂ (24.26 grams) was charged to thefeed (5.85 grams) to produce a ZrO₂/feed mixture. The resulting mixturecatalyst was metered to the reactor vessel over 20 minutes (a calculatedWHSV of 0.6 h⁻¹) to maintain the feed liquid level of 50% of the reactorvolume under a nitrogen atmosphere. Once an internal temperature of thereactor reached 734° C., methane and water (24.1 grams charged as steam)were charged to the reaction vessel over 20 minutes. The reaction wasrun until little or no gas and/or liquid product was produced. Thereactor was weighed at the end of the run to obtain a final reactorweight.

The total product included 0.4 grams of a crude product, and 5.25 gramsof gas. The gas included 0.881 grams of non-condensable hydrocarbons,2.989 grams of CO₂, 1.832 grams of CO, 0.469 grams of H₂ gas, and 0.34grams of H₂S. From the difference in the initial and final weight of thereactor 1.67 grams of coke was formed. The molar ratio of CO to CO₂ wascalculated to be 1.

The selectivity for products containing carbon was calculated based onthe weight of carbon containing products divided by weight of asphaltcharged to the reactor. For two experiments run as described in Example26 the mean selectivity for products containing carbon was determined tobe: 31.73 wt % for combined carbon monoxide and carbon dioxide, 18.93 wt% for non-condensable hydrocarbons and 10.34 wt % for crude product and39 wt % for coke.

This example demonstrates that contacting a feed with a catalyst supportin the presence of a hydrogen source and steam produces a minimal amountof crude product, gases, and coke.

Comparative Example 27 Contact of a Feed with a Hydrogen Source underNon-Catalytic Conditions to Produce a Crude Product

The feed and apparatus was the same as described in Example 24. Siliconcarbide, an inert material, (silicon carbide, 13.1 grams) was placed onthe screen in the reactor.

The feed was heated to 150° C. Silicon carbide (24.26 grams) was chargedto the feed (4.96 grams) to produce a silicon carbide/feed mixture. Theresulting mixture catalyst was metered to the reactor vessel over 0.5hour (a calculated WHSV of 0.4 h⁻¹) to maintain the feed liquid level of50% of the reactor volume under a nitrogen atmosphere. Once an internaltemperature of the reactor reached 725° C., methane and water (24.1grams charged as steam) were charged to the reaction vessel over 0.5hour. The reaction was run until little or no gas and/or liquid productwas produced. The reactor was weighed at the end of the run to obtain afinal reactor weight.

The total product included 0.222 grams of a crude product, and 1.467grams of gas. The gas included 0.248 grams of non-condensablehydrocarbons, 0.61 grams (0.014 moles) of CO₂, 0.513 grams (0.018 moles)of CO, and 0.091 grams of H₂ gas. From the difference in the initial andfinal weight of the reactor 3.49 grams of coke was formed.

This example demonstrates that contacting a feed with a hydrogen sourceand steam produces a greater amount of coke than when the feed iscontacted with an inorganic salt catalyst and a catalyst support in thepresence of a hydrogen source and steam.

The selectivity for products containing carbon was calculated based onthe weight of carbon containing products divided by weight of asphaltcharged to the reactor. For two experiments run as described in Example27 the mean selectivity for products containing carbon was determined tobe: 11.75 wt % for combined carbon monoxide and carbon dioxide, 7.99 wt% for non-condensable hydrocarbons and 9.32 wt % for crude product and65.96 wt % for coke.

The mean selectivity for the products that contain carbon for Examples24-27 is depicted in FIG. 16. Data points 270 represents the totalamount of carbon monoxide and carbon dioxide gases produced. Data points272 represents amount of non-condensable hydrocarbons produced. Datapoints 274 represents amount of crude product. Data points 276represents amount of coke produced and/or unreacted asphaltenes. Asshown in FIG. 16, the total amount of carbon monoxide and carbon dioxidegases is enhanced when a feed is contacted with an inorganic saltcatalyst as compared to contact with a catalyst support or under thermalconditions. When calcium oxide is used as the inorganic salt catalystmore crude product is produced compared to magnesium oxide, zirconiumoxide, or the thermal experiment. Thus, selection of catalyst andcontrolling the contacting conditions at a temperature of at most 1000°C. allows the composition of the total product to be adjusted. Inaddition, controlling the contacting conditions limited the conversionof feed to total hydrocarbons is at most 50%, based on the molar amountof carbon in the feed.

Example 28 Contact of a Feed with a Hydrogen Source in the Presence of aSupported Inorganic Catalyst

An inorganic salt catalyst was supported on zeolite. The supportedinorganic salt catalyst contained, per gram of supported inorganic saltcatalyst, 0.049 grams of potassium, 0.069 grams of rubidium, and 0.109grams of cesium. The inorganic catalyst had a surface area 5.3 m²/g atp/p0=0.03, an external surface area of 3.7 m²/g, and a pore volume of0.22 ml/g. A feed (Kuwait long residue, WHSV of 1 h⁻¹) was fluidlycontacted with a supported inorganic salt catalyst (modified Equilibriumc) in a micro-activity test (“MAT”) at 450° C., 1 bar absolute (0.1 MPA)in the presence of steam (water flow rate of 0.36 gram/min to producethe steam) using methane as the fluidization gas at a rate of 45 NmL/minto produce a total product. Five runs were performed with each runhaving a different catalyst to feed ratio of 3, 4, 5, 6, 7, and 8. Theamount of gas, crude product, and coke formed for each run is tabulatedin Table 2, FIG. 17 and graphically depicted in FIG. 18. Plot 280represents the amount of gas produced. Plot 282 represents the amount ofcrude product produced, and Plot 284 represents the amount of cokeproduced for each run.

As shown in this example contacting a feed with a supported inorganicsalt catalyst produced in the presence of a hydrogen source and steamproduced a total product and at most 0.2 grams of coke. At a catalyst tofeed ratio 4, a total product that included 0.08 grams of gas, 0.73grams of crude product and 0.16 grams of coke, per gram of feed, wasproduced. At a catalyst to feed ratio of 8, a total product thatincluded 0.09 grams of gas, 0.7 grams of crude product and 0.14 grams ofcoke, per gram of feed, was produced. As shown, adjusting the catalystto feed ratio from 4 to 8 lowered the amount of coke formed duringcontacting.

Comparative Example 29 Contact of a Feed with a Hydrogen Source in thePresence of an E-Cat at Various Catalyst/Feed Ratios

The equipment, contacting conditions, feed, and catalyst to feed ratioswere the same as for Example 28. The catalyst was a commercialEquilibrium fluidized catalytic cracking catalyst (“E-Cat”, Akzo NobelCobra 553) that included 1541 ppmw of nickel, 807 ppmw of vanadium, 029wt % sodium and 0.4 wt % iron. The E-Cat had a surface area of 163 m²/gat p/p0=3, an external surface areas of 26.3 m²/g, and a pore volume of0.37 ml/g. The amount of gas, crude product, and coke formed for eachrun is tabulated in Table 3, FIG. 17 and graphically depicted in FIG.18. Plot 286 represents the amount of gas produced. Plot 288 representsthe amount of crude product produced, and Plot 290 represents the amountof coke produced for each run.

As shown in this comparative example, the amount of gas and crudeproduct formed from the feed using the new E-Cat remained constant forat various catalyst to feed ratios. At an E-Cat to feed ratio of 4, 0.23grams of gas, 0.60 grams of crude product, and 0.16 grams of coke ofproduct, per gram of feed, was produced. At an E-Cat to feed ratio of 8,0.26 grams of feed, 0.43 grams of crude product, and 0.21 grams of coke,per gram of feed, was produced.

In this patent, certain U.S. patents have been incorporated byreference. The text of such U.S. patents is, however, only incorporatedby reference to the extent that no conflict exists between such text andthe other statements and drawings set forth herein. In the event of suchconflict, then any such conflicting text in such incorporated byreference U.S. patents is specifically not incorporated by reference inthis patent.

Further modifications and alternative embodiments of various aspects ofthe invention will be apparent to those skilled in the art in view ofthis description. Accordingly, this description is to be construed asillustrative only and is for the purpose of teaching those skilled inthe art the general manner of carrying out the invention. It is to beunderstood that the forms of the invention shown and described hereinare to be taken as examples of embodiments. Elements and materials maybe substituted for those illustrated and described herein, parts andprocesses may be reversed and certain features of the invention may beutilized independently, all as would be apparent to one skilled in theart after having the benefit of this description of the invention.Changes may be made in the elements described herein without departingfrom the spirit and scope of the invention as described in the followingclaims.

1. A method of producing a total product, comprising: continuouslycontacting a feed with a hydrogen source in the presence of one or moreinorganic salt catalysts and steam to produce a total product, whereinthe feed has at least 0.02 grams of sulfur, per gram of feed; andproducing a total product that includes coke and the crude product,wherein the crude product has a sulfur content of at most 90% of thesulfur content of the feed and the content of coke is at most 0.2 grams,per gram of feed.
 2. The method of claim 1, wherein at least one of theinorganic salt catalysts comprises one or more alkaline-earth metalsand/or one or more compounds of one or more alkaline-earth metals. 3.The method of claim 1, wherein at least one of the inorganic saltcatalysts comprises one or more alkali metals and/or one or morecompounds of one or more alkali metals.
 4. The method of claim 1,wherein the inorganic salt catalyst comprises one or more alkali metals,one or more compounds of one or more alkali metals, one or morealkaline-earth metals, one or more compounds of one or morealkaline-earth metals or combinations thereof.
 5. The method of claim 1,wherein at least one of the inorganic salt catalysts is limestone and/ordolomite.
 6. The method of claim 1, wherein at least one of theinorganic salt catalysts is supported, and the support compriseslimestone, carbon, coke, nonvolatile charcoal, activated carbon, flyash, dolomite, clay, TiO₂, ZrO₂, aluminosilicate, spent hydroprocessingcatalyst, metals and/or compounds of metals recovered from the a totalproduct/feed mixture, one or more metals from Columns 5-10 of thePeriodic Table, one or more compounds of one or more metals from Columns5-10 of the Periodic Table, or combinations thereof.
 7. The method ofclaim 1, wherein at least one of the inorganic salt catalysts comprisesone or more metal sulfides.
 8. The method of claim 1, wherein at leastone of the inorganic salt catalysts comprises nickel sulfide and/orvanadium sulfide.
 9. The method of claim 1, wherein contactingconditions comprise controlling temperature in a range from about 300°C. to about 1000° C.
 10. The method of claim 1, wherein contactingconditions comprise controlling temperature in a range from about 400°C. to about 900° C.
 11. The method of claim 1, wherein contactingconditions comprise controlling temperature in a range from about 500°C. to about 800° C.
 12. The method of claim 1, wherein the hydrogensource comprises methane, hydrogen gas, hydrocarbons having a carbonnumber of at most 6, or combinations thereof.
 13. The method of claim 1,wherein the contacting zone is a circulating fluidized bed and/or acirculating fluidized riser.
 14. The method of claim 1, wherein the feedhas a total asphaltenes content of at least 0.01 grams of asphaltenesper gram of feed.
 15. The method of claim 1, wherein the feed has atotal residue content of at least 0.01 grams per gram of feed.
 16. Themethod of claim 1, wherein the feed has at least 0.5 grams ofhydrocarbons having a boiling point below 538° C., per gram of feed. 17.The method of claim 1, wherein the contacting is performed in thepresence of hydrogen sulfide.
 18. The method of claim 1, furthercomprising providing the total product to a separation zone, wherein thetotal product is separated into crude product and/or gas.
 19. The methodof claim 1, wherein the total product comprises syngas.
 20. The methodof claim 1, wherein the total product comprises carbon oxide gases andhydrogen.
 21. The method of claim 1, wherein the total product includesa crude product and the crude product has greater than 0 grams, but lessthan 0.01 grams of the inorganic salt catalysts.
 22. The method of claim1, wherein the total product comprises a crude product, and the methodfurther comprises fractionating the crude product into one or moredistillate fractions, and producing transportation fuel from at leastone of the distillate fractions.